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zO=-(kA%^`7I~aavU|=}H5O>?HcrNxZgyslhQhAa zRzD-aYn?eZ2U=a<%D}K|Q|n~#N@E8zD@PGw2>#qKgfVPvJ9sl3JjS)D;l~{e46arp z>up_Z9V~Cz+FC;I{v{ri@ii75fMb%8fq``s9u_7#o*yy%+zCFO=5$@qF!U4yn3NxX zo-xxKJKi;MFuSecDyo K{07^>r~d;FJ4)&R diff --git a/Manuscript/QUESTDB.bib b/Manuscript/QUESTDB.bib index 0b6d79b..40cbd52 100644 --- a/Manuscript/QUESTDB.bib +++ b/Manuscript/QUESTDB.bib @@ -1,13 +1,636 @@ %% This BibTeX bibliography file was created using BibDesk. %% http://bibdesk.sourceforge.net/ -%% Created for Pierre-Francois Loos at 2020-06-15 10:37:34 +0200 +%% Created for Pierre-Francois Loos at 2020-09-04 10:26:50 +0200 %% Saved with string encoding Unicode (UTF-8) +@misc{Benali_2020, + Archiveprefix = {arXiv}, + Author = {Anouar Benali and Kevin Gasperich and Kenneth D. Jordan and Thomas Applencourt and Ye Luo and M. Chandler Bennett and Jaron T. Krogel and Luke Shulenburger and Paul R. C. Kent and Pierre-Fran{\c c}ois Loos and Anthony Scemama and Michel Caffarel}, + Date-Added = {2020-09-04 10:00:38 +0200}, + Date-Modified = {2020-09-04 10:00:48 +0200}, + Eprint = {2007.11673}, + Primaryclass = {physics.chem-ph}, + Title = {Towards a Systematic Improvement of the Fixed-Node Approximation in Diffusion Monte Carlo for Solids}, + Year = {2020}} + +@misc{Scemama_2020, + Archiveprefix = {arXiv}, + Author = {Anthony Scemama and Emmanuel Giner Anouar Benali and Pierre-Fran{\c c}ois Loos}, + Date-Added = {2020-09-04 09:59:46 +0200}, + Date-Modified = {2020-09-04 10:00:38 +0200}, + Eprint = {2008.10088}, + Primaryclass = {physics.chem-ph}, + Title = {Taming the fixed-node error in diffusion Monte Carlo via range separation}, + Year = {2020}} + +@article{Li_2020, + Author = {Li, Junhao and Yao, Yuan and Holmes, Adam A. and Otten, Matthew and Sun, Qiming and Sharma, Sandeep and Umrigar, C. J.}, + Date-Added = {2020-09-04 09:50:25 +0200}, + Date-Modified = {2020-09-04 09:50:32 +0200}, + Doi = {10.1103/PhysRevResearch.2.012015}, + Issue = {1}, + Journal = {Phys. Rev. Research}, + Month = {Jan}, + Numpages = {6}, + Pages = {012015}, + Publisher = {American Physical Society}, + Title = {Accurate many-body electronic structure near the basis set limit: Application to the chromium dimer}, + Url = {https://link.aps.org/doi/10.1103/PhysRevResearch.2.012015}, + Volume = {2}, + Year = {2020}, + Bdsk-Url-1 = {https://link.aps.org/doi/10.1103/PhysRevResearch.2.012015}, + Bdsk-Url-2 = {https://doi.org/10.1103/PhysRevResearch.2.012015}} + +@misc{Yao_2020, + Archiveprefix = {arXiv}, + Author = {Yuan Yao and Emmanuel Giner and Junhao Li and Julien Toulouse and C. J. Umrigar}, + Date-Added = {2020-09-04 09:49:40 +0200}, + Date-Modified = {2020-09-04 09:49:50 +0200}, + Eprint = {2004.10059}, + Primaryclass = {physics.chem-ph}, + Title = {Almost exact energies for the Gaussian-2 set with the semistochastic heat-bath configuration interaction method}, + Year = {2020}} + +@misc{Loos_2020e, + Archiveprefix = {arXiv}, + Author = {Pierre-Fran{\c c}ois Loos and Yann Damour and Anthony Scemama}, + Date-Added = {2020-09-04 09:47:52 +0200}, + Date-Modified = {2020-09-04 09:48:02 +0200}, + Eprint = {2008.11145}, + Primaryclass = {physics.chem-ph}, + Title = {Note: The performance of CIPSI on the ground state electronic energy of benzene}, + Year = {2020}} + +@article{Send_2011a, + Abstract = { We compile a 109-membered benchmark set of adiabatic excitation energies (AEEs) from high-resolution gas-phase experiments. Our data set includes a variety of organic chromophores with up to 46 atoms, radicals, and inorganic transition metal compounds. Many of the 91 molecules in our set are relevant to atmospheric chemistry, photovoltaics, photochemistry, and biology. The set samples valence, Rydberg, and ionic states of various spin multiplicities. As opposed to vertical excitation energies, AEEs are rigorously defined by energy differences of vibronic states, directly observable, and insensitive to errors in equilibrium structures. We supply optimized ground state and excited state structures, which allows fast and convenient evaluation of AEEs with two single-point energy calculations per system. We apply our benchmark set to assess the performance of time-dependent density functional theory using common semilocal functionals and the configuration interaction singles method. Hybrid functionals such as B3LYP and PBE0 yield the best results, with mean absolute errors around 0.3 eV. We also investigate basis set convergence and correlations between different methods and between the magnitude of the excited state relaxation energy and the AEE error. A smaller, 15-membered subset of AEEs is introduced and used to assess the correlated wave function methods CC2 and ADC(2). These methods improve upon hybrid TDDFT for systems with single-reference ground states but perform less well for radicals and small-gap transition metal compounds. None of the investigated methods reaches ``chemical accuracy'' of 0.05 eV in AEEs. }, + Author = {Send, Robert and K{\"u}hn, Michael and Furche, Filipp}, + Date-Added = {2020-09-04 09:11:20 +0200}, + Date-Modified = {2020-09-04 09:11:44 +0200}, + Doi = {10.1021/ct200272b}, + Journal = {J. Chem. Theory Comput.}, + Number = {8}, + Pages = {2376-2386}, + Title = {Assessing Excited State Methods by Adiabatic Excitation Energies}, + Volume = {7}, + Year = {2011}, + Bdsk-Url-1 = {http://pubs.acs.org/doi/abs/10.1021/ct200272b}, + Bdsk-Url-2 = {http://dx.doi.org/10.1021/ct200272b}} + +@article{Winter_2013, + Abstract = {In the present study a benchmark set of medium-sized and large aromatic organic molecules with 10--78 atoms is presented. For this test set 0--0 transition energies measured in supersonic jets are compared to those calculated with DFT and the B3LYP functional{,} ADC(2){,} CC2 and the spin-scaled CC2 variants SOS-CC2 and SCS-CC2. Geometries of the ground and excited states have been optimized with these methods in polarized triple zeta basis sets. Zero-point vibrational corrections have been calculated with the same methods and basis sets. In addition the energies have been corrected by single point calculations with a triple zeta basis augmented with diffuse functions{,} aug-cc-pVTZ. The deviations of the theoretical results from experimental electronic origins{,} which have all been measured in the gas phase with high-resolution techniques{,} were evaluated. The accuracy of SOS-CC2 is comparable to that of unscaled CC2{,} whereas ADC(2) has slightly larger errors. The lowest errors were found for SCS-CC2. All correlated wave function methods provide significantly better results than DFT with the B3LYP functional. The effects of the energy corrections from the augmented basis set and the method-consistent calculation of the zero-point vibrational corrections are small. With this benchmark set reliable reference data for 0--0 transition energies for larger organic chromophores are available that can be used to benchmark the accuracy of other quantum chemical methods such as new DFT functionals or semi-empirical methods for excitation energies and structures and thereby augments available benchmark sets augments present benchmark sets which include mainly smaller molec}, + Author = {Winter, Nina O. C. and Graf, Nora K. and Leutwyler, Samuel and H{\"a}ttig, Christof}, + Date-Added = {2020-09-04 09:09:39 +0200}, + Date-Modified = {2020-09-04 09:09:45 +0200}, + Doi = {10.1039/C2CP42694C}, + Issue = {18}, + Journal = {Phys. Chem. Chem. Phys.}, + Pages = {6623-6630}, + Publisher = {The Royal Society of Chemistry}, + Title = {Benchmarks for 0--0 Transitions of Aromatic Organic Molecules: DFT/B3LYP{,} ADC(2){,} CC2{,} SOS-CC2 and SCS-CC2 Compared to High-resolution Gas-Phase Data}, + Url = {http://dx.doi.org/10.1039/C2CP42694C}, + Volume = {15}, + Year = {2013}, + Bdsk-Url-1 = {http://dx.doi.org/10.1039/C2CP42694C}} + +@article{Kohn_2003, + Author = {K{\"o}hn, Andreas and H{\"a}ttig, Christof}, + Date-Added = {2020-09-04 09:09:07 +0200}, + Date-Modified = {2020-09-04 09:09:17 +0200}, + Doi = {http://dx.doi.org/10.1063/1.1597635}, + Journal = {J. Chem. Phys.}, + Number = {10}, + Pages = {5021--5036}, + Title = {Analytic Gradients for Excited States in the Coupled-Cluster Model CC2 Employing the Resolution-Of-The-Identity Approximation}, + Url = {http://scitation.aip.org/content/aip/journal/jcp/119/10/10.1063/1.1597635}, + Volume = {119}, + Year = {2003}, + Bdsk-Url-1 = {http://scitation.aip.org/content/aip/journal/jcp/119/10/10.1063/1.1597635}, + Bdsk-Url-2 = {http://dx.doi.org/10.1063/1.1597635}} + +@article{Schriber_2017, + Author = {Schriber, Jeffrey B. and Evangelista, Francesco A.}, + Date-Added = {2020-09-03 21:56:17 +0200}, + Date-Modified = {2020-09-03 21:56:17 +0200}, + Doi = {10.1021/acs.jctc.7b00725}, + Journal = {J. Chem. Theory Comput.}, + Month = {Oct}, + Publisher = {American Chemical Society}, + Title = {{Adaptive Configuration Interaction for Computing Challenging Electronic Excited States with Tunable Accuracy}}, + Year = {2017}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jctc.7b00725}} + +@article{Li_2018, + Author = {J. Li and M. Otten and A. A. Holmes and S. Sharma and C. J. Umrigar}, + Date-Added = {2020-09-03 21:55:13 +0200}, + Date-Modified = {2020-09-03 21:55:13 +0200}, + Doi = {10.1063/1.5055390}, + Journal = {J. Chem. Phys.}, + Pages = {214110}, + Title = {Fast semistochastic heat-bath configuration interaction}, + Volume = {149}, + Year = {2018}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.5055390}} + +@article{Coe_2014, + Author = {Coe, J.P. and Murphy, P. and Paterson, M.J.}, + Date-Added = {2020-09-03 21:55:04 +0200}, + Date-Modified = {2020-09-03 21:55:04 +0200}, + Doi = {10.1016/j.cplett.2014.04.050}, + File = {/Users/loos/Zotero/storage/69HR6V3N/Coe14.pdf}, + Issn = {00092614}, + Journal = {Chem. Phys. Lett.}, + Language = {en}, + Month = jun, + Pages = {46-52}, + Shorttitle = {Applying {{Monte Carlo}} Configuration Interaction to Transition Metal Dimers}, + Title = {Applying {{Monte Carlo}} Configuration Interaction to Transition Metal Dimers: {{Exploring}} the Balance between Static and Dynamic Correlation}, + Volume = {604}, + Year = {2014}, + Bdsk-Url-1 = {https://doi.org/10.1016/j.cplett.2014.04.050}} + +@article{Coe_2018, + Author = {J. P. Coe}, + Date-Added = {2020-09-03 21:55:04 +0200}, + Date-Modified = {2020-09-03 21:55:04 +0200}, + Doi = {10.1021/acs.jctc.8b00849}, + Journal = {J. Chem. Theory Comput.}, + Pages = {5739}, + Title = {Machine Learning Configuration Interaction}, + Volume = {14}, + Year = {2018}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jctc.8b00849}} + +@article{Dash_2019, + Author = {Dash, Monika and Feldt, Jonas and Moroni, Saverio and Scemama, Anthony and Filippi, Claudia}, + Date-Added = {2020-09-03 21:54:25 +0200}, + Date-Modified = {2020-09-03 21:54:25 +0200}, + Doi = {10.1021/acs.jctc.9b00476}, + Issn = {1549-9618}, + Journal = {J. Chem. Theory Comput.}, + Month = {Sep}, + Number = {9}, + Pages = {4896--4906}, + Publisher = {American Chemical Society}, + Title = {{Excited States with Selected Configuration Interaction-Quantum Monte Carlo: Chemically Accurate Excitation Energies and Geometries}}, + Volume = {15}, + Year = {2019}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jctc.9b00476}} + +@misc{Eriksen_2020, + Archiveprefix = {arXiv}, + Author = {Janus J. Eriksen and Tyler A. Anderson and J. Emiliano Deustua and Khaldoon Ghanem and Diptarka Hait and Mark R. Hoffmann and Seunghoon Lee and Daniel S. Levine and Ilias Magoulas and Jun Shen and Norman M. Tubman and K. Birgitta Whaley and Enhua Xu and Yuan Yao and Ning Zhang and Ali Alavi and Garnet Kin-Lic Chan and Martin Head-Gordon and Wenjian Liu and Piotr Piecuch and Sandeep Sharma and Seiichiro L. Ten-no and C. J. Umrigar and J{\"u}rgen Gauss}, + Date-Added = {2020-09-03 21:52:47 +0200}, + Date-Modified = {2020-09-03 21:52:47 +0200}, + Eprint = {2008.02678}, + Primaryclass = {physics.chem-ph}, + Title = {The Ground State Electronic Energy of Benzene}, + Year = {2020}} + +@article{Tubman_2016, + Author = {Tubman, Norm M. and Lee, Joonho and Takeshita, Tyler Y. and {Head-Gordon}, Martin and Whaley, K. Birgitta}, + Date-Added = {2020-09-03 21:52:47 +0200}, + Date-Modified = {2020-09-03 21:52:47 +0200}, + Doi = {10.1063/1.4955109}, + File = {/Users/loos/Zotero/storage/VDKR3CTF/Tubman16.pdf}, + Issn = {0021-9606, 1089-7690}, + Journal = {J. Chem. Phys.}, + Language = {en}, + Month = jul, + Number = {4}, + Pages = {044112}, + Title = {A Deterministic Alternative to the Full Configuration Interaction Quantum {{Monte Carlo}} Method}, + Volume = {145}, + Year = {2016}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.4955109}} + +@misc{Tubman_2018, + Archiveprefix = {arXiv}, + Author = {Norm M. Tubman and Daniel S. Levine and Diptarka Hait and Martin Head-Gordon and K. Birgitta Whaley}, + Date-Added = {2020-09-03 21:52:47 +0200}, + Date-Modified = {2020-09-03 21:52:47 +0200}, + Eprint = {1808.02049}, + Primaryclass = {cond-mat.str-el}, + Title = {An efficient deterministic perturbation theory for selected configuration interaction methods}, + Year = {2018}} + +@article{Tubman_2020, + Author = {Tubman, N. M. and Freeman, C. D. and Levine, D. S. and Hait, D. and Head-Gordon, M. and Whaley, K. B.}, + Date-Added = {2020-09-03 21:52:47 +0200}, + Date-Modified = {2020-09-03 21:52:47 +0200}, + Doi = {10.1021/acs.jctc.8b00536}, + Journal = {J. Chem. Theory Comput.}, + Pages = {2139}, + Title = {Modern Approaches to Exact Diagonalization and Selected Configuration Interaction with the Adaptive Sampling CI Method}, + Volume = {16}, + Year = {2020}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jctc.8b00536}} + +@article{Scemama_2013, + Author = {Scemama, Anthony and Caffarel, Michel and Oseret, Emmanuel and Jalby, William}, + Date-Added = {2020-09-03 21:52:30 +0200}, + Date-Modified = {2020-09-03 21:52:30 +0200}, + Doi = {10.1002/jcc.23216}, + Journal = {J. Comput. Chem.}, + Pages = {938--951}, + Title = {{Quantum Monte Carlo for large chemical systems: Implementing efficient strategies for petascale platforms and beyond}}, + Volume = {34}, + Year = {2013}, + Bdsk-Url-1 = {https://doi.org/10.1002/jcc.23216}} + +@misc{Scemama_2015, + Author = {Scemama, Anthony and Giner, Emmanuel and Applencourt, Thomas and Caffarel, Michel}, + Date-Added = {2020-09-03 21:52:30 +0200}, + Date-Modified = {2020-09-03 21:52:30 +0200}, + Doi = {10.13140/RG.2.1.3187.9766}, + Howpublished = {Pacifichem, Advances in Quantum Monte Carlo}, + Month = {Dec}, + Title = {{QMC using very large configuration interaction-type expansions}}, + Year = {2015}, + Bdsk-Url-1 = {https://doi.org/10.13140/RG.2.1.3187.9766}} + +@article{Scemama_2016, + Author = {Scemama, Anthony and Applencourt, Thomas and Giner, Emmanuel and Caffarel, Michel}, + Date-Added = {2020-09-03 21:52:30 +0200}, + Date-Modified = {2020-09-03 21:52:30 +0200}, + Doi = {10.1002/jcc.24382}, + Issn = {0192-8651}, + Journal = {J. Comput. Chem.}, + Month = {Jun}, + Number = {20}, + Pages = {1866--1875}, + Publisher = {Wiley-Blackwell}, + Title = {Quantum Monte Carlo with very large multideterminant wavefunctions}, + Url = {http://dx.doi.org/10.1002/jcc.24382}, + Volume = {37}, + Year = {2016}, + Bdsk-Url-1 = {http://dx.doi.org/10.1002/jcc.24382}} + +@article{Scemama_2018, + Author = {Scemama, Anthony and Garniron, Yann and Caffarel, Michel and Loos, Pierre-Fran{\c c}ois}, + Date-Added = {2020-09-03 21:52:30 +0200}, + Date-Modified = {2020-09-03 21:52:30 +0200}, + Doi = {10.1021/acs.jctc.7b01250}, + Issn = {1549-9618}, + Journal = {J. Chem. Theory Comput.}, + Month = {Mar}, + Number = {3}, + Pages = {1395--1402}, + Publisher = {American Chemical Society}, + Title = {{Deterministic Construction of Nodal Surfaces within Quantum Monte Carlo: The Case of FeS}}, + Volume = {14}, + Year = {2018}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jctc.7b01250}} + +@article{Scemama_2018b, + Author = {Scemama, Anthony and Benali, Anouar and Jacquemin, Denis and Caffarel, Michel and Loos, Pierre-Fran{\c c}ois}, + Date-Added = {2020-09-03 21:52:30 +0200}, + Date-Modified = {2020-09-03 21:52:30 +0200}, + Doi = {10.1063/1.5041327}, + Issn = {0021-9606}, + Journal = {J. Chem. Phys.}, + Month = {Jul}, + Number = {3}, + Pages = {034108}, + Publisher = {American Institute of Physics}, + Title = {{Excitation energies from diffusion Monte Carlo using selected configuration interaction nodes}}, + Volume = {149}, + Year = {2018}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.5041327}} + +@article{Scemama_2019, + Author = {A. Scemama and M. Caffarel and A. Benali and D. Jacquemin and P. F. Loos.}, + Date-Added = {2020-09-03 21:52:30 +0200}, + Date-Modified = {2020-09-03 21:52:30 +0200}, + Doi = {10.1016/j.rechem.2019.100002}, + Journal = {Res. Chem.}, + Pages = {100002}, + Title = {Influence of pseudopotentials on excitation energies from selected configuration interaction and diffusion Monte Carlo}, + Volume = {1}, + Year = {2019}, + Bdsk-Url-1 = {https://doi.org/10.1016/j.rechem.2019.100002}} + +@article{Caffarel_2016a, + Author = {Caffarel, Michel and Applencourt, Thomas and Giner, Emmanuel and Scemama, Anthony}, + Date-Added = {2020-09-03 21:51:56 +0200}, + Date-Modified = {2020-09-03 21:51:56 +0200}, + Doi = {10.1063/1.4947093}, + Issn = {0021-9606}, + Journal = {J. Chem. Phys.}, + Month = {Apr}, + Number = {15}, + Pages = {151103}, + Publisher = {American Institute of Physics}, + Title = {{Communication: Toward an improved control of the fixed-node error in quantum Monte Carlo: The case of the water molecule}}, + Volume = {144}, + Year = {2016}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.4947093}} + +@article{Casanova_Paes_2020, + Author = {M. Casanova-Paez and L. Goerigk}, + Date-Added = {2020-09-02 12:01:37 +0200}, + Date-Modified = {2020-09-02 12:02:23 +0200}, + Doi = {10.1063/5.0018354}, + Journal = {J. Chem. Phys.}, + Pages = {064106}, + Title = {Assessing the Tamm--Dancoff approximation, singlet--singlet, and singlet--triplet excitations with the latest long-range corrected double-hybrid density functionals}, + Volume = {153}, + Year = {2020}, + Bdsk-Url-1 = {https://doi.org/10.1063/5.0018354}} + +@article{Casanova-Paez_2019, + Author = {M. Casanova-Paez and M. B. Dardis and L. Goerigk}, + Date-Added = {2020-09-02 11:59:59 +0200}, + Date-Modified = {2020-09-02 12:01:35 +0200}, + Doi = {10.1021/acs.jctc.9b00013}, + Journal = {J. Chem. Theory Comput.}, + Pages = {4735}, + Title = {$\omega$B2PLYP and $\omega$B2GPPLYP: The First Two Double-Hybrid Density Functionals with Long-Range Correction Optimized for Excitation Energies}, + Volume = {15}, + Year = {2019}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jctc.9b00013}} + +@article{Schwabe_2017, + Author = {T. Schwabe and L. Goerigk}, + Date-Added = {2020-09-02 11:57:54 +0200}, + Date-Modified = {2020-09-02 11:58:54 +0200}, + Doi = {10.1021/acs.jctc.7b00386}, + Journal = {J. Chem. Theory Comput.}, + Pages = {4307}, + Title = {Time-Dependent Double-Hybrid Density Functionals with Spin-Component and Spin-Opposite Scaling}, + Volume = {13}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jctc.7b00386}} + +@article{Loos_2020d, + Author = {Loos, Pierre-Francois and Jacquemin, Denis}, + Date-Added = {2020-09-01 22:50:44 +0200}, + Date-Modified = {2020-09-01 22:51:03 +0200}, + Doi = {10.1021/acs.jpclett.9b03652}, + Eprint = {https://doi.org/10.1021/acs.jpclett.9b03652}, + Journal = {J. Phys. Chem. Lett.}, + Number = {3}, + Pages = {974--980}, + Title = {Is ADC(3) as Accurate as CC3 for Valence and Rydberg Transition Energies?}, + Url = {https://doi.org/10.1021/acs.jpclett.9b03652}, + Volume = {11}, + Year = {2020}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jpclett.9b03652}} + +@article{Leang_2012, + Author = {Leang,Sarom S. and Zahariev,Federico and Gordon,Mark S.}, + Date-Added = {2020-09-01 13:54:26 +0200}, + Date-Modified = {2020-09-01 13:55:18 +0200}, + Doi = {10.1063/1.3689445}, + Eprint = {https://doi.org/10.1063/1.3689445}, + Journal = {The Journal of Chemical Physics}, + Number = {10}, + Pages = {104101}, + Title = {Benchmarking the performance of time-dependent density functional methods}, + Url = {https://doi.org/10.1063/1.3689445}, + Volume = {136}, + Year = {2012}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.3689445}} + +@article{Zhao_2006, + Author = {Zhao,Yan and Truhlar,Donald G.}, + Date-Added = {2020-09-01 13:52:35 +0200}, + Date-Modified = {2020-09-01 13:52:45 +0200}, + Doi = {10.1063/1.2202732}, + Eprint = {https://doi.org/10.1063/1.2202732}, + Journal = {The Journal of Chemical Physics}, + Number = {22}, + Pages = {224105}, + Title = {Comparative assessment of density functional methods for 3d transition-metal chemistry}, + Url = {https://doi.org/10.1063/1.2202732}, + Volume = {124}, + Year = {2006}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.2202732}} + +@article{Kozma_2020, + Author = {B. Kozma and A. Tajti and B. Demoulin and R. Izsak and M. Nooijen and P. G. Szalay}, + Date-Added = {2020-09-01 13:50:03 +0200}, + Date-Modified = {2020-09-01 13:58:43 +0200}, + Doi = {10.1021/acs.jctc.0c00154}, + Journal = {J. Chem. Theory Comput.}, + Pages = {4213--4225}, + Title = {A New Benchmark Set for Excitation Energy of Charge Transfer States: Systematic Investigation of Coupled Cluster Type Methods}, + Volume = {16}, + Year = {2020}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jctc.0c00154}} + +@article{Williams_2020, + Author = {Williams, Kiel T and Yao, Yuan and Li, Jia and Chen, Li and Shi, Hao and Motta, Mario and Niu, Chunyao and Ray, Ushnish and Guo, Sheng and Anderson, Robert J and others}, + Date-Added = {2020-09-01 13:30:18 +0200}, + Date-Modified = {2020-09-01 13:30:18 +0200}, + Doi = {10.1103/PhysRevX.10.011041}, + Journal = {Phys. Rev. X}, + Number = {1}, + Pages = {011041}, + Title = {Direct comparison of many-body methods for realistic electronic Hamiltonians}, + Volume = {10}, + Year = {2020}, + Bdsk-Url-1 = {https://doi.org/10.1103/PhysRevX.10.011041}} + +@article{Motta_2017, + Author = {Motta, Mario and Ceperley, David M and Chan, Garnet Kin-Lic and Gomez, John A and Gull, Emanuel and Guo, Sheng and Jim{\'e}nez-Hoyos, Carlos A and Lan, Tran Nguyen and Li, Jia and Ma, Fengjie and others}, + Date-Added = {2020-09-01 13:30:09 +0200}, + Date-Modified = {2020-09-01 13:30:09 +0200}, + Doi = {10.1103/PhysRevX.7.031059}, + Journal = {Phys. Rev. X}, + Number = {3}, + Pages = {031059}, + Title = {Towards the solution of the many-electron problem in real materials: Equation of state of the hydrogen chain with state-of-the-art many-body methods}, + Volume = {7}, + Year = {2017}, + Bdsk-Url-1 = {https://doi.org/10.1103/PhysRevX.7.031059}} + +@article{Leblanc_2015, + Author = {LeBlanc, J. P. F. and Antipov, Andrey E and Becca, Federico and Bulik, Ireneusz W and Chan, Garnet Kin-Lic and Chung, Chia-Min and Deng, Youjin and Ferrero, Michel and Henderson, Thomas M and Jim{\'e}nez-Hoyos, Carlos A and others}, + Date-Added = {2020-09-01 13:29:44 +0200}, + Date-Modified = {2020-09-01 13:29:44 +0200}, + Doi = {10.1103/PhysRevX.5.041041}, + Journal = {Phys. Rev. X}, + Number = {4}, + Pages = {041041}, + Title = {Solutions of the two-dimensional hubbard model: benchmarks and results from a wide range of numerical algorithms}, + Volume = {5}, + Year = {2015}, + Bdsk-Url-1 = {https://doi.org/10.1103/PhysRevX.5.041041}} + +@book{JensenBook, + Address = {New York}, + Author = {F. Jensen}, + Date-Added = {2020-09-01 10:35:29 +0200}, + Date-Modified = {2020-09-01 10:36:20 +0200}, + Edition = {3rd}, + Keywords = {qmech}, + Publisher = {Wiley}, + Title = {Introduction to Computational Chemistry}, + Year = {2017}} + +@article{Loos_2019a, + Author = {P. F. Loos and D. Jacquemin}, + Date-Added = {2020-08-31 21:57:32 +0200}, + Date-Modified = {2020-08-31 21:58:34 +0200}, + Doi = {10.1021/acs.jctc.8b01103}, + Journal = {J. Chem. Theory Comput.}, + Pages = {2481}, + Title = {Chemically Accurate 0-0 Energies With not-so-Accurate Excited State Geometries}, + Volume = {15}, + Year = {2019}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jctc.8b01103}} + +@article{Loos_2018, + Author = {Loos, Pierre-Fran{\c c}ois and Galland, Nicolas and Jacquemin, Denis}, + Date-Added = {2020-08-31 21:56:45 +0200}, + Date-Modified = {2020-08-31 21:56:45 +0200}, + Doi = {10.1021/acs.jpclett.8b02058}, + Journal = {J. Phys. Chem. Lett.}, + Number = {16}, + Pages = {4646--4651}, + Title = {Theoretical 0--0 Energies with Chemical Accuracy}, + Volume = {9}, + Year = {2018}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jpclett.8b02058}} + +@article{Stuke_2020, + Author = {Annika Stuke and Christian Kunkel and Dorothea Golze and Milica Todorovi{\'c} and Johannes T. Margraf and Karsten Reuter and Patrick Rinke and Harald Oberhofer}, + Date-Added = {2020-08-31 15:12:43 +0200}, + Date-Modified = {2020-08-31 15:12:43 +0200}, + Doi = {10.1038/s41597-020-0385-y}, + Journal = {Sci. Data}, + Pages = {58}, + Title = {Atomic Structures and Orbital Energies of 61,489 Crystal-Forming Organic Molecules}, + Volume = {7}, + Year = {2020}, + Bdsk-Url-1 = {https://doi.org/10.1038/s41597-020-0385-y}} + +@article{Tajti_2004, + Author = {Tajti,Attila and Szalay,P{\'e}ter G. and Cs{\'a}sz{\'a}r,Attila G. and K{\'a}llay,Mih{\'a}ly and Gauss,J{\"u}rgen and Valeev,Edward F. and Flowers,Bradley A. and V{\'a}zquez,Juana and Stanton,John F.}, + Date-Added = {2020-08-31 14:12:23 +0200}, + Date-Modified = {2020-08-31 14:12:30 +0200}, + Doi = {10.1063/1.1811608}, + Eprint = {https://doi.org/10.1063/1.1811608}, + Journal = {The Journal of Chemical Physics}, + Number = {23}, + Pages = {11599-11613}, + Title = {HEAT: High accuracy extrapolated ab initio thermochemistry}, + Url = {https://doi.org/10.1063/1.1811608}, + Volume = {121}, + Year = {2004}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.1811608}} + +@article{Bomble_2006, + Author = {Bomble,Yannick J. and V{\'a}zquez,Juana and K{\'a}llay,Mih{\'a}ly and Michauk,Christine and Szalay,P{\'e}ter G. and Cs{\'a}sz{\'a}r,Attila G. and Gauss,J{\"u}rgen and Stanton,John F.}, + Date-Added = {2020-08-31 14:11:45 +0200}, + Date-Modified = {2020-08-31 14:11:52 +0200}, + Doi = {10.1063/1.2206789}, + Eprint = {https://doi.org/10.1063/1.2206789}, + Journal = {The Journal of Chemical Physics}, + Number = {6}, + Pages = {064108}, + Title = {High-accuracy extrapolated ab initio thermochemistry. II. Minor improvements to the protocol and a vital simplification}, + Url = {https://doi.org/10.1063/1.2206789}, + Volume = {125}, + Year = {2006}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.2206789}} + +@article{Rezac_2011, + Author = {{\v R}ez{\'a}{\v c}, Jan and Riley, Kevin E. and Hobza, Pavel}, + Date-Added = {2020-08-31 14:06:07 +0200}, + Date-Modified = {2020-08-31 14:08:52 +0200}, + Doi = {10.1021/ct2002946}, + Eprint = {https://doi.org/10.1021/ct2002946}, + Journal = {Journal of Chemical Theory and Computation}, + Note = {PMID: 21836824}, + Number = {8}, + Pages = {2427-2438}, + Title = {S66: A Well-balanced Database of Benchmark Interaction Energies Relevant to Biomolecular Structures}, + Url = {https://doi.org/10.1021/ct2002946}, + Volume = {7}, + Year = {2011}, + Bdsk-Url-1 = {https://doi.org/10.1021/ct2002946}} + +@article{Jureka_2006, + Abstract = {MP2 and CCSD(T) complete basis set (CBS) limit interaction energies and geometries for more than 100 DNA base pairs{,} amino acid pairs and model complexes are for the first time presented together. Extrapolation to the CBS limit is done by using two-point extrapolation methods and different basis sets (aug-cc-pVDZ -- aug-cc-pVTZ{,} aug-cc-pVTZ -- aug-cc-pVQZ{,} cc-pVTZ -- cc-pVQZ) are utilized. The CCSD(T) correction term{,} determined as a difference between CCSD(T) and MP2 interaction energies{,} is evaluated with smaller basis sets (6-31G** and cc-pVDZ). Two sets of complex geometries were used{,} optimized or experimental ones. The JSCH-2005 benchmark set{,} which is now available to the chemical community{,} can be used for testing lower-level computational methods. For the first screening the smaller training set (S22) containing 22 model complexes can be recommended. In this case larger basis sets were used for extrapolation to the CBS limit and also CCSD(T) and counterpoise-corrected MP2 optimized geometries were sometimes adopted.}, + Author = {Jure{\v c}ka, Petr and {\v S}poner, Ji{\v r}{\'\i} and {\v C}ern{\'y}, Ji{\v r}{\'\i} and Hobza, Pavel}, + Date-Added = {2020-08-31 14:04:15 +0200}, + Date-Modified = {2020-08-31 14:05:40 +0200}, + Doi = {10.1039/B600027D}, + Issue = {17}, + Journal = {Phys. Chem. Chem. Phys.}, + Pages = {1985-1993}, + Publisher = {The Royal Society of Chemistry}, + Title = {Benchmark database of accurate (MP2 and CCSD(T) complete basis set limit) interaction energies of small model complexes{,} DNA base pairs{,} and amino acid pairs}, + Url = {http://dx.doi.org/10.1039/B600027D}, + Volume = {8}, + Year = {2006}, + Bdsk-Url-1 = {http://dx.doi.org/10.1039/B600027D}} + +@article{Curtiss_1997, + Author = {Curtiss,Larry A. and Raghavachari,Krishnan and Redfern,Paul C. and Pople,John A.}, + Date-Added = {2020-08-31 13:53:50 +0200}, + Date-Modified = {2020-08-31 13:53:58 +0200}, + Doi = {10.1063/1.473182}, + Eprint = {https://doi.org/10.1063/1.473182}, + Journal = {The Journal of Chemical Physics}, + Number = {3}, + Pages = {1063-1079}, + Title = {Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation}, + Url = {https://doi.org/10.1063/1.473182}, + Volume = {106}, + Year = {1997}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.473182}} + +@article{Curtiss_2007, + Author = {Curtiss,Larry A. and Redfern,Paul C. and Raghavachari,Krishnan}, + Date-Added = {2020-08-31 13:47:30 +0200}, + Date-Modified = {2020-08-31 13:47:36 +0200}, + Doi = {10.1063/1.2436888}, + Eprint = {https://doi.org/10.1063/1.2436888}, + Journal = {The Journal of Chemical Physics}, + Number = {8}, + Pages = {084108}, + Title = {Gaussian-4 theory}, + Url = {https://doi.org/10.1063/1.2436888}, + Volume = {126}, + Year = {2007}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.2436888}} + +@article{Curtiss_1998, + Author = {Curtiss,Larry A. and Raghavachari,Krishnan and Redfern,Paul C. and Rassolov,Vitaly and Pople,John A.}, + Date-Added = {2020-08-31 13:46:42 +0200}, + Date-Modified = {2020-08-31 13:46:53 +0200}, + Doi = {10.1063/1.477422}, + Eprint = {https://doi.org/10.1063/1.477422}, + Journal = {The Journal of Chemical Physics}, + Number = {18}, + Pages = {7764-7776}, + Title = {Gaussian-3 (G3) theory for molecules containing first and second-row atoms}, + Url = {https://doi.org/10.1063/1.477422}, + Volume = {109}, + Year = {1998}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.477422}} + +@article{Pople_1989, + Author = {Pople,John A. and Head‐Gordon,Martin and Fox,Douglas J. and Raghavachari,Krishnan and Curtiss,Larry A.}, + Date-Added = {2020-08-31 13:45:32 +0200}, + Date-Modified = {2020-08-31 13:45:46 +0200}, + Doi = {10.1063/1.456415}, + Eprint = {https://doi.org/10.1063/1.456415}, + Journal = {The Journal of Chemical Physics}, + Number = {10}, + Pages = {5622-5629}, + Title = {Gaussian‐1 theory: A general procedure for prediction of molecular energies}, + Url = {https://doi.org/10.1063/1.456415}, + Volume = {90}, + Year = {1989}, + Bdsk-Url-1 = {https://doi.org/10.1063/1.456415}} + @article{Christiansen_1995a, Author = {Ove Christiansen and Henrik Koch and Poul J{\o}rgensen}, Date-Added = {2020-06-10 22:40:39 +0200}, @@ -783,6 +1406,7 @@ Title = {Many-Body Effective Energy Theory: Photoemission at Strong Correlation}, Volume = {15}, Year = {2019}, + Bdsk-File-1 = {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}, Bdsk-Url-1 = {https://doi.org/10.1021/acs.jctc.9b00427}} @article{Dreuw_2005, @@ -1584,22 +2208,6 @@ Year = {2019}, Bdsk-Url-1 = {https://doi.org/10.21468/SciPostPhys.6.4.040}} -@article{Li_2020, - Author = {Jing Li and Ivan Duchemin and Xavier Blase and Valerio Olevano}, - Date-Added = {2020-05-18 21:40:28 +0200}, - Date-Modified = {2020-05-18 21:40:28 +0200}, - Doi = {10.21468/SciPostPhys.8.2.020}, - Issue = {2}, - Journal = {SciPost Phys.}, - Pages = {20}, - Publisher = {SciPost}, - Title = {{Ground-state correlation energy of beryllium dimer by the Bethe-Salpeter equation}}, - Url = {https://scipost.org/10.21468/SciPostPhys.8.2.020}, - Volume = {8}, - Year = {2020}, - Bdsk-Url-1 = {https://scipost.org/10.21468/SciPostPhys.8.2.020}, - Bdsk-Url-2 = {https://doi.org/10.21468/SciPostPhys.8.2.020}} - @article{Linden_1988, Author = {von der Linden, Wolfgang and Horsch, Peter}, Date-Added = {2020-05-18 21:40:28 +0200}, @@ -1682,7 +2290,8 @@ Pages = {2374--2383}, Title = {The Quest for Highly-Accurate Excitation Energies: a Computational Perspective}, Volume = {11}, - Year = {2020}} + Year = {2020}, + Bdsk-Url-1 = {https://doi.org/10.1021/acs.jpclett.0c00014}} @article{Lu_2017, Abstract = {We present a new cubic scaling algorithm for the calculation of the RPA correlation energy. Our scheme splits up the dependence between the occupied and virtual orbitals in χ0 by use of Cauchy's integral formula. This introduces an additional integral to be carried out, for which we provide a geometrically convergent quadrature rule. Our scheme also uses the newly developed Interpolative Separable Density Fitting algorithm to further reduce the computational cost in a way analogous to that of the Resolution of Identity method.}, @@ -1840,10 +2449,10 @@ Year = {2013}, Bdsk-Url-1 = {http://dx.doi.org/10.1039/C3CS00007A}} -@article{QP2, +@article{Garniron_2019, Author = {Y. Garniron and K. Gasperich and T. Applencourt and A. Benali and A. Fert{\'e} and J. Paquier and B. Pradines and R. Assaraf and P. Reinhardt and J. Toulouse and P. Barbaresco and N. Renon and G. David and J. P. Malrieu and M. V{\'e}ril and M. Caffarel and P. F. Loos and E. Giner and A. Scemama}, Date-Added = {2020-05-18 21:40:28 +0200}, - Date-Modified = {2020-05-18 21:40:28 +0200}, + Date-Modified = {2020-09-03 21:54:11 +0200}, Doi = {10.1021/acs.jctc.9b00176}, Journal = {J. Chem. Theory Comput.}, Pages = {3591}, @@ -6826,16 +7435,6 @@ Year = {2000}, Bdsk-Url-1 = {https://doi.org/10.1021/jp992518z}} -@article{Leang_2012, - Author = {Leang, Sarom S. and Zahariev, Federico and Gordon, Mark S.}, - Date-Added = {2020-01-01 21:36:51 +0100}, - Date-Modified = {2020-01-01 21:36:52 +0100}, - Journal = {J. Chem. Phys.}, - Pages = {104101}, - Title = {Benchmarking the Performance of Time-Dependent Density Functional Methods}, - Volume = {136}, - Year = {2012}} - @article{Lee_2011a, Author = {Lee, R. M. and Drummond, N. D.}, Date-Added = {2020-01-01 21:36:51 +0100}, @@ -9444,23 +10043,6 @@ Year = {2011}, Bdsk-Url-1 = {http://dx.doi.org/10.1021/ct1005938}} -@article{Scemama_2013, - Author = {Scemama, Anthony and Caffarel, Michel and Oseret, Emmanuel and Jalby, William}, - Date-Added = {2020-01-01 21:36:51 +0100}, - Date-Modified = {2020-01-01 21:36:52 +0100}, - Doi = {10.1002/jcc.23216}, - Issn = {0192-8651}, - Journal = {J. Comput. Chem.}, - Month = {Jan}, - Number = {11}, - Pages = {938--951}, - Publisher = {Wiley-Blackwell}, - Title = {Quantum Monte Carlo for large chemical systems: Implementing efficient strategies for petascale platforms and beyond}, - Url = {http://dx.doi.org/10.1002/jcc.23216}, - Volume = {34}, - Year = {2013}, - Bdsk-Url-1 = {http://dx.doi.org/10.1002/jcc.23216}} - @article{Scemama_2014, Author = {Scemama, A. and Applencourt, T. and Giner, E. and Caffarel, M.}, Date-Added = {2020-01-01 21:36:51 +0100}, @@ -9478,35 +10060,6 @@ Year = {2014}, Bdsk-Url-1 = {http://dx.doi.org/10.1063/1.4903985}} -@article{Scemama_2016, - Author = {Scemama, Anthony and Applencourt, Thomas and Giner, Emmanuel and Caffarel, Michel}, - Date-Added = {2020-01-01 21:36:51 +0100}, - Date-Modified = {2020-01-01 21:36:52 +0100}, - Doi = {10.1002/jcc.24382}, - Issn = {0192-8651}, - Journal = {J. Comput. Chem.}, - Month = {Jun}, - Number = {20}, - Pages = {1866--1875}, - Publisher = {Wiley-Blackwell}, - Title = {Quantum Monte Carlo with very large multideterminant wavefunctions}, - Url = {http://dx.doi.org/10.1002/jcc.24382}, - Volume = {37}, - Year = {2016}, - Bdsk-Url-1 = {http://dx.doi.org/10.1002/jcc.24382}} - -@article{Scemama_2018, - Author = {A. Scemama and Y. Garniron and M. Caffarel and P. F. Loos}, - Date-Added = {2020-01-01 21:36:51 +0100}, - Date-Modified = {2020-04-12 10:01:48 +0200}, - Doi = {10.1021/acs.jctc.7b01250}, - Journal = {J. Chem. Theory Comput.}, - Pages = {1395}, - Title = {Deterministic Construction of Nodal Surfaces Within Quantum Monte Carlo: The Case of FeS}, - Volume = {14}, - Year = {2018}, - Bdsk-Url-1 = {https://doi.org/10.1021/acs.jctc.7b01250}} - @article{Schapiro_2014, Author = {Schapiro, Igor and Neese, Frank}, Date-Added = {2020-01-01 21:36:51 +0100}, @@ -9732,10 +10285,10 @@ Year = {2010}, Bdsk-Url-1 = {https://doi.org/10.1103/PhysRevA.81.012508}} -@article{Send_2011, +@article{Send_2011b, Author = {Send, R. and Valsson, O. and Filippi, C.}, Date-Added = {2020-01-01 21:36:51 +0100}, - Date-Modified = {2020-01-01 21:36:52 +0100}, + Date-Modified = {2020-09-04 09:11:47 +0200}, Journal = {J. Chem. Theory Comput.}, Number = {2}, Pages = {444--455}, @@ -10418,23 +10971,6 @@ Volume = {94}, Year = {2005}} -@article{Tubman_2016, - Author = {Tubman, Norm M. and Lee, Joonho and Takeshita, Tyler Y. and Head-Gordon, Martin and Whaley, K. Birgitta}, - Date-Added = {2020-01-01 21:36:51 +0100}, - Date-Modified = {2020-01-01 21:36:52 +0100}, - Doi = {10.1063/1.4955109}, - Issn = {1089-7690}, - Journal = {J. Chem. Phys.}, - Month = {Jul}, - Number = {4}, - Pages = {044112}, - Publisher = {AIP Publishing}, - Title = {A deterministic alternative to the full configuration interaction quantum Monte Carlo method}, - Url = {http://dx.doi.org/10.1063/1.4955109}, - Volume = {145}, - Year = {2016}, - Bdsk-Url-1 = {http://dx.doi.org/10.1063/1.4955109}} - @article{Tuna_2015, Author = {Tuna, Deniz and Lefrancois, Daniel and Wola\'nski, \L{}ukasz and Gozem, Samer and Schapiro, Igor and Andruni\'ow, Tadeusz and Dreuw, Andreas and Olivucci, Massimo}, Date-Added = {2020-01-01 21:36:51 +0100}, diff --git a/Manuscript/QUEST_WIREs.tex b/Manuscript/QUEST_WIREs.tex index 7ac65db..180c548 100644 --- a/Manuscript/QUEST_WIREs.tex +++ b/Manuscript/QUEST_WIREs.tex @@ -16,10 +16,12 @@ % Add additional packages here if required \usepackage{siunitx} +\usepackage{mhchem} % macros \newcommand{\ra}{\rightarrow} \newcommand{\pis}{\pi^*} +\newcommand{\double}{\text{double}} \newcommand{\ie}{\textit{i.e.}} \newcommand{\eg}{\textit{e.g.}} \newcommand{\alert}[1]{\textcolor{red}{#1}} @@ -28,6 +30,7 @@ \newcommand{\fnt}{\footnotetext} \newcommand{\tabc}[1]{\multicolumn{1}{c}{#1}} \newcommand{\QP}{\textsc{quantum package}} +\newcommand{\SupInf}{supporting information} % Update article type if known \papertype{Review Article} @@ -43,6 +46,7 @@ % Use the \authfn to add symbols for additional footnotes and present addresses, if any. Usually start with 1 for notes about author contributions; then continuing with 2 etc if any author has a different present address. \author[1]{Mickael V\'eril} \author[1]{Anthony Scemama} +\author[1]{Michel Caffarel} \author[2]{Filippo Lipparini} \author[1]{Martial Boggio-Pasqua} \author[1]{Pierre-Fran\c{c}ois Loos} @@ -70,8 +74,13 @@ \maketitle \begin{abstract} -This is the abstract. - +We describe our efforts of the last few years to create a mega set of more than \alert{470} highly-accurate vertical excitation energies of various natures ($\pi \to \pis$, $n \to \pis$, double excitation, Rydberg, singlet, doublet, triplet, etc) for small- and medium-sized molecules. +These values have been obtained using a combination of high-order coupled cluster and selected configuration interaction calculations using increasingly large diffuse basis sets. +One of the key aspect of the so-called QUEST dataset of vertical excitations is that it does not rely on any experimental values, avoiding potential biases inherently linked to experiments and facilitating in the process theoretical comparisons for a given basis set. +Following this composite protocol, we have been able to produce theoretical best estimate (TBEs) at the aug-cc-pVTZ level and near the complete basis set limit for each of these transitions. +These TBEs have been employed to benchmark a large number of wave function methods such as CIS(D), ADC(2), STEOM-CCSD, EOM-CCSD, CCSDR(3), CCSDT-3, ADC(3), CC3, CASPT2, NEVPT2, and others. +In order to gather the huge number of data produced during the QUEST project, we have created a website where one can easily test and compare the accuracy of a given method with respect to various variables such as the molecule size or its family, the nature of the excited state, the size of the basis set, and many others. +We hope that the present review will provide a useful summary of our work so far. % Please include a maximum of seven keywords \keywords{Excited states, full configuration interaction, excitation energies} \end{abstract} @@ -80,25 +89,81 @@ This is the abstract. \section{Introduction} %%%%%%%%%%%%%%%%%%%%%%%%%%%%% -Excited states are important \citep{Loos_2020a}. -\begin{figure}[bt] - \centering - \includegraphics[width=0.5\linewidth]{example-image-rectangle} - \caption{This is the caption.} -\end{figure} +Nowadays, there exists a very large number of electronic structure computational approaches, more or less expensive depending on their overall accuracy, able to quantitatively predict the absolute and/or relative energies of electronic states in molecular systems \cite{JensenBook}. +One important aspect of some of these theoretical methods is their ability to access the energies of electronic excited states, i.e., states that have higher total energies than the so-called ground state (that is, the lowest-energy state). +The faithful description of excited states are particularly challenging from a theoretical point of view and is key to a deeper understanding of photochemical and photophysical processes like absorption, fluorescence, or even chemoluminescence \cite{Bernardi_1996,Olivucci_2010,Robb_2007,Navizet_2011}. +For a given level of theory, ground-state methods are usually more accurate than their excited-state analog. +The reasons behind this are (at least) twofold: i) one might lack a proper variational principle for excited-state energies, and ii) excited states are often very close in energy from each other but they can have very different natures ($\pi \to \pis$, $n \to \pis$, charge transfer, double excitation, valence, Rydberg, singlet, doublet, triplet, etc). +Designing excited-state methods which can tackle on the same footing all these types of excited states at an affordable cost remain an open challenge in theoretical computational chemistry \cite{Gonzales_2012, Loos_2020a}. + +When one designs a new theoretical model, the first feature that one might want to test is its overall accuracy, i.e., its ability to reproduce reference (or benchmark) values for a given system in a well-defined setup (same geometry, same basis set, etc). +These values can be absolute or relative energies, geometrical parameters, physical or chemical properties, etc, extracted from experiments, high-level theoretical calculations, or a combination of both. +To do so, the electronic structure community has designed along the years benchmark sets, i.e., sets of molecules for which one could (very) accurately computed theoretical estimates and/or access solid experimental data for given properties. +Regarding ground-states properties, two of the oldest and most employed sets are probably the Gaussian-1 and Gaussian-2 benchmark sets \cite{Pople_1989,Curtiss_1991,Curtiss_1997} developed by the group of Pople in the 1990's which gathers atomization energies, ionization energies, electron affinities, proton affinities, bond dissociation energies, and reaction barriers. +Another very useful set for the design of methods able to catch dispersion effects is the S22 benchmark set \cite{Jureka_2006} (and its extended S66 version \cite{Rezac_2011}) of Hobza and collaborators which provides benchmark interaction energies for weakly-interacting (non covalent) systems. +One could also mentioned the $GW$100 set \cite{vanSetten_2015,Krause_2015,Maggio_2016} (and its $GW$5000 extension \cite{Stuke_2020}) of ionization energies which has helped enormously the community to settle on the implementation of $GW$-type methods for molecular systems \cite{vanSetten_2013,Bruneval_2016,Caruso_2016,Govoni_2018}. +The extrapolated ab initio thermochemistry (HEAT) designed to achieve high accuracy for enthalpies of formation of atoms and small molecules (without experimental data) is another successful example of benchmak set \cite{Tajti_2004,Bomble_2006,Harding_2008}. +More recently, the benchmark datasets provided by the \textit{Simons Collaboration on the Many-Electron Problem} have been extremely valuable to the community by providing, for example, highly-accurate ground state energies for hydrogen chains \cite{Motta_2017} and transition metal atoms and their ions and monoxides \cite{Williams_2020}. +Let us also mention the set of Zhao and Truhlar for small transition metal complexes \cite{Zhao_2006}, and the Gagliardi-Truhlar set \cite{Hoyer_2016} employed to compare the accuracy of multiconfiguration pair-density functional theory against the well-established CASPT2 method \cite{Andersson_1990,Andersson_1992,Roos,Roos_1996}. + +The examples presented above are all designed for ground-state properties, and there exists now specific protocols designed to accurately model excited-state energies and properties. +Benchmark datasets of excited-state energies and/or properties are less numerous than their ground-state counterparts but their number have been growing at a consistent pace in the last few years. +Below, we provide a short description of some of these. +One the most characteristic example is the benchmark set of vertical excitations proposed by Thiel and coworkers \cite{Schreiber_2008,Silva-Junior_2008,Silva-Junior_2010,Silva-Junior_2010b,Silva-Junior_2010c}. +The so-called Thiel (or M\"ulheim) set of excitation energies gathers a large number of excitation energies determined in 28 medium-size organic molecules with a total of 223 valence excited states (152 singlet and 71 triplet states) for which theoretical best estimates (TBEs) were defined. +In their first study, Thiel and collaborators performed CC2, CCSD, CC3, and CASPT2 calculations (with the TZVP basis) on MP2/6-31G(d) geometries in order to provide (based on additional high-quality literature data) TBEs for these transitions \cite{Silva-Junior_2010b}. +These TBEs were quickly refined with the larger aug-cc-pVTZ basis set, highlighting the importance of diffuse functions in the faithful description of excited states (especially for Rydberg states). +In the same spirit, it is also worth mentioning Gordon's set of vertical transitions (based on experimental values) used to benchmark the performance of TD-DFT \cite{Leang_2012}, as well as its extended version by the Goerigk and coworkers \cite{Schwabe_2017,Casanova-Paez_2019,Casanova_Paes_2020} who decided to replace the experimental reference values by CC3 excitation energies instead. +A new benchmark set of charge-transfer excited states was recently introduced by Szalay and coworkers based on coupled cluster methods \cite{Kozma_2020}. + +Following a similar philosophy, we have recently reported in several studies highly-accurate vertical excitations for small- and medium-sized molecules \cite{Loos_2020a,Loos_2018a,Loos_2019,Loos_2020b,Loos_2020c}. +One of the key aspect of the so-called QUEST dataset of vertical excitations which we will describe in details in the present review article is that it does not rely on any experimental values, avoiding potential biases inherently linked to experiments and facilitating in the process theoretical comparisons. +Moreover, our protocol has been designed to be as uniform as possible, which means that we use a very systematic procedure for all excited states in order to make cross-comparison as straightforward as possible. +Importantly, it allowed us to benchmark a series of popular excited-state wave function methods partially or fully accounting for double and triple excitations as well as multiconfigurational methods such as CASPT2 and NEVPT2. +In the same vein, we have also produced chemically-accurate theoretical 0-0 energies \cite{Loos_2018,Loos_2019a,Loos_2019b} which can be more straightforwardly compare to experimental data \cite{Kohn_2003,Send_2011a,Winter_2013}. +We refer the interested reader to Ref.~\cite{Loos_2019b} where we review the generic benchmark studies devoted to adiabatic and 0-0 energies performed in the last two decades. + +The QUEST dataset has the particularity to be based in a large proportion on selected configuration interaction (SCI) reference excitation energies as well as high-order CC methods such as CCSDT and CCSDTQ. +Recently, SCI methods have been a force to reckon with for the computation of highly-accurate energies in small- and medium-sized molecules \cite{Holmes_2017,Chien_2018,Loos_2018a,Li_2018,Loos_2019,Loos_2020b,Loos_2020c,Loos_2020a,Li_2020,Eriksen_2020,Loos_2020e,Yao_2020}. +The SCI family is composed by numerous members \cite{Bender_1969,Whitten_1969,Huron_1973,Abrams_2005,Bunge_2006,Bytautas_2009,Giner_2013,Caffarel_2014,Giner_2015,Garniron_2017b,Caffarel_2016a,Caffarel_2016b,Holmes_2016,Sharma_2017,Holmes_2017,Chien_2018,Scemama_2018,Scemama_2018b,Garniron_2018,Evangelista_2014,Schriber_2016,Schriber_2017,Liu_2016,Per_2017,Ohtsuka_2017,Zimmerman_2017,Li_2018,Ohtsuka_2017,Coe_2018,Loos_2019} and their fundamental philosophy consists, roughly speaking, in retaining only the most energetically relevant determinants of the FCI space following a given criterion to avoid the exponential increase of the size of the CI expansion. + +Originally developed in the late 1960's by Bender and Davidson \cite{Bender_1969} as well as Whitten and Hackmeyer, \cite{Whitten_1969} new efficient SCI algorithms have resurfaced recently. +Four examples are adaptive sampling CI (ASCI) \cite{Tubman_2016,Tubman_2018,Tubman_2020}, iCI \cite{Liu_2016}, semistochastic heat-bath CI (SHCI) \cite{Holmes_2016,Holmes_2017,Sharma_2017,Li_2018}), and \textit{Configuration Interaction using a Perturbative Selection made Iteratively} (CIPSI), \cite{Huron_1973} +These four flavors of SCI includes a second-order perturbative (PT2) correction which is key to estimate the ``distance'' to the genuine FCI solution. +The QUEST set of excitation energies relies on the CIPSI algorithm, which is, from a historical point of view, one of the oldest SCI algorithm. +It was developed in 1973 by Huron, Rancurel, and Malrieu \cite{Huron_1973} (see also Refs.~\cite{Evangelisti_1983,Cimiraglia_1985,Cimiraglia_1987,Illas_1988,Povill_1992}). +Recently, the determinant-driven CIPSI algorithm has been efficiently implemented \cite{Giner_2013,Giner_2015} in the open-source programming environment {\QP} by our group enabling to perform massively parallel computations \cite{Garniron_2017,Garniron_2018,Garniron_2019,Loos_2020e}. +CIPSI is also frequently used to provide accurate trial wave function for QMC calculations in molecules \cite{Caffarel_2014,Caffarel_2016a,Caffarel_2016b,Giner_2013,Giner_2015,Scemama_2015,Scemama_2016,Scemama_2018,Scemama_2018b,Scemama_2019,Dash_2018,Dash_2019,Scemama_2020} and more recently for periodic solids \cite{Benali_2020}. +We refer the interested reader to Ref.~\cite{Garniron_2019} where one can find all the details regarding the implementation of the CIPSI algorithm. + +The present article is organized as follows. +In Sec.~\ref{sec:tools}, we detail the specificities of our protocol by providing the computational details regarding geometries, basis sets, (reference and benchmarked) computational methods, the list of Electronic structure software we have employed, and a new way of estimating rigorously the extrapolation error in SCI calculations. +We then describe in Sec.~\ref{sec:QUEST} the content of our five QUEST sub-sets providing for each of them the number of reference excitation energies, the list of benchmarked methods as well as other specificities. +A special emphasis is placed on our latest add-on, QUEST\#5, specifically designed for the present manuscript where we have considered, in particular but not only, larger molecules as well as additional FCI values for five- and six-membered rings. +Section \ref{sec:TBE} discusses the generation of the TBEs, while Sec.~\ref{sec:bench} proposes a comprehensive benchmark of various methods on the entire QUEST set which is composed by more than \alert{470} excitations with, in addition, a specific analysis for each type of excited states. +Section \ref{sec:website} describe the feature of the website of the specifically designed to gather the entire data generated during these last few years. +Thanks to this website, one can easily test and compare the accuracy of a given method with respect to various variables such as the molecule size or its family, the nature of the excited state, the size of the basis set, and many others. +Finally, we draw our conclusions in Sec.~\ref{sec:ccl}. %%%%%%%%%%%%%%%%%%%%%%%%%%%%% \section{Computational tools} +\label{sec:tools} %%%%%%%%%%%%%%%%%%%%%%%%%%%%% %======================= \subsection{Geometries} %======================= +The molecules included in the QUEST dataset have been systematically optimized at the CC3/aug-cc-pVTZ level of theory, except for a very few cases. +As shown in Refs.~\cite{Hattig_2005c,Budzak_2017}, CC3 provides extremely accurate ground- and excited-state geometries. +For the present review article, we have gathered all the geometries in the {\SupInf}. +\footnote{These geometries can be found at...} %======================= \subsection{Basis sets} %======================= +In the entire set, we use one Pople basis set [6-31+G(d)], the augmented family of Dunning basis sets aug-cc-pVXZ (where X $=$ D, T, Q, and 5), and sometimes its doubly- and triply-augmented variants, d-aug-cc-pVXZ and t-aug-cc-pVXZ respectively. +Doubly- and triply-augmented basis sets are usually employed for Rydberg states where it is not uncommon to observe a strong basis set dependence due to the very diffuse nature of these excited states. %================================== \subsection{Computational methods} @@ -107,61 +172,210 @@ Excited states are important \citep{Loos_2020a}. %------------------------------------------------ \subsubsection{Reference computational methods} %------------------------------------------------ +In order to compute reference vertical energies, we have designed different strategies depending on the actual nature of the transition and the size of the system. +For small systems (typically 1--3 non-hydrogen atoms), we resort to SCI methods which can provide near-FCI excitation energies for compact basis sets. +Obviously, the smaller the molecule, the larger the basis we can afford. +For larger systems (\ie, 4--6 non-hydrogen atom), one cannot afford SCI calculations anymore expect in a few exceptions, and we then rely on CC theory (CCSDT and CCSDTQ typically) to obtain accurate transition energies. %------------------------------------------------ \subsubsection{Benchmarked computational methods} %------------------------------------------------ +%------------------------------------------------ +\subsubsection{Electronic structure software} +%------------------------------------------------ + +%------------------------------------------------ +\subsubsection{Estimating the extrapolation error} +%------------------------------------------------ + +\alert{Here comes Anthony's part on error bars in SCI methods.} + %%%%%%%%%%%%%%%%%%%%%%%%%%%%% \section{The QUEST database} +\label{sec:QUEST} %%%%%%%%%%%%%%%%%%%%%%%%%%%%% %======================= \subsection{Overview} %======================= - +The QUEST database gathers more than \alert{470} highly-accurate excitation energies of various natures (valence, Rydberg, $n \ra \pis$, $\pi \ra \pis$, singlet, triplet, doublet, and double excitations) for molecules ranging from diatomics to ... %======================= \subsection{QUEST\#1} %======================= +The QUEST\#1 benchmark set \cite{Loos_2018a} consists of 110 vertical excitation energies (as well as oscillator strengths) from 18 molecules with sizes ranging from one to three non-hydrogen atoms (water, hydrogen sulfide, ammonia, hydrogen chloride, dinitrogen, carbon monoxide, acetylene, ethylene, formaldehyde, methanimine, thioformaldehyde, acetaldehyde, cyclopropene, diazomethane, formamide, ketene, nitrosomethane, and the smallest +streptocyanine). For this set, we provided two sets of TBEs: i) one obtained within the frozen-core approximation and the aug-cc-pVTZ basis set, and ii) another one including further corrections for basis set incompleteness and ``all electron'' effects. +For the former set, we systematically selected FCI/aug-cc-pVTZ values to define our TBEs except in very few cases. +For the latter set, both the ``all electron'' correlation and the basis set corrections were systematically obtained at the CC3 level of theory and with the d-aug-cc-pV5Z basis for the nine smallest molecules, and slightly more compact basis sets for the larger compounds. +Our TBE/aug-cc-pVTZ reference excitation energies were employed to benchmark a series of popular excited-state wave function methods partially or fully accounting for double and triple excitations, namely CIS(D), CC2, CCSD, STEOM-CCSD, CCSDR(3), CCSDT- CC3, ADC(2), and ADC(3). +Our main conclusions were that i) ADC(2) and CC2 show strong similarities in terms of accuracy, ii) STEOM-CCSD is, on average, as accurate as CCSD, the latter overestimating transition energies, iii) CC3 is extremely accurate (with a mean absolute error of only $\sim 0.03$ eV) and that although slightly less accurate than CC3, CCSDT-3 could be used as a reliable reference for benchmark studies, and iv) ADC(3) was found to be significantly less accurate than CC3 by overcorrecting ADC(2) excitation energies. %======================= \subsection{QUEST\#2} %======================= +The QUEST\#2 benchmark set \cite{Loos_2019} reports reference energies for double excitations. +This set gathers 20 vertical transitions from 14 small- and medium-size molecules (acrolein, benzene, beryllium atom, butadiene, carbon dimer and trimer, ethylene, formaldehyde, glyoxal, hexatriene, nitrosomethane, nitroxyl, pyrazine, and tetrazine). +The TBEs of the QUEST\#2 set are obtained with SCI and/or multiconfigurational [CASSCF, CASPT2, (X)MS-CASPT2, and NEVPT2] calculations depending on the size of the molecules and the level of theory that we could afford. +An important addition to this second study was the inclusion of various flavors of multiconfigurational methods (CASSCF, CASPT2, and NEVPT2) in addition to high-order CC methods including, at least, perturbative triples (CC3, CCSDT, CCSDTQ, etc). +Our results demonstrated that the error of CC methods is intimately linked to the amount of double-excitation character in the vertical transition. +For ``pure'' double excitations (i.e., for transitions which do not mix with single excitations), the error in CC3 and CCSDT can easily reach $1$ and $0.5$ eV, respectively, while it goes down to a few tenths of an eV for more common transitions (such as in butadiene and benzene) involving a significant amount of single excitations. +The quality of the excitation energies obtained with CASPT2 and NEVPT2 was harder to predict as the overall accuracy of these methods is highly dependent on both the system and the selected active space. +Nevertheless, these two methods were found to be more accurate for transition with a small percentage of single excitations (error usually below $0.1$ eV) than for excitations dominated by single excitations where the error is closer from $0.1$--$0.2$ eV %======================= \subsection{QUEST\#3} %======================= - +The QUEST\#3 benchmark set \cite{Loos_2020b} is, by far, our largest set, and consists of highly accurate vertical transition energies obtained for 27 molecules encompassing 4, 5, and 6 non-hydrogen atoms (acetone, acrolein, benzene, butadiene, cyanoacetylene, cyanoformaldehyde, cyanogen, cyclopentadiene, cyclopropenone, cyclopropenethione, diacetylene, furan, glyoxal, imidazole, isobutene, methylenecyclopropene, propynal, pyrazine, pyridazine, pyridine, pyrimidine, pyrrole, tetrazine, thioacetone, thiophene, thiopropynal, and triazine) for a total of 238 vertical transition energies and 90 oscillator strengths with a reasonably good balance between singlet, triplet, valence, and Rydberg excited states. +For these 238 transitions, we have estimated that 224 are chemically accurate for the considered geometry. +To define the TBEs of the QUEST\#3 set, we employed CC methods up to the highest technically possible order (CC3, CCSDT, and CCSDTQ), and, when affordable SCI calculations with very large reference spaces (up to hundred million determinants in certain cases), as well as the most reliable multiconfigurational method, NEVPT2, for double excitations. +Most of our TBEs are based on CCSDTQ (4 non-hydrogen atoms) or CCSDT (5 and 6 non-hydrogen atoms) excitation energies. +For all the transitions of the QUEST\#3 set, we reported at least CCSDT/aug-cc-pVTZ (sometimes with basis set extrapolation) and CC3/aug-cc-pVQZ transition energies as well as CC3/aug-cc-pVTZ oscillator strengths for each dipole-allowed transition. +Pursuing our previous benchmarking efforts, we confirmed that CC3 almost systematically delivers transition energies in agreement with higher-level theoretical models ($\pm0.04$ eV) except for transitions presenting a dominant double-excitation character where multiconfigurational methods like NEVPT2 have clearly the edge. +This settles down, at least for now, the debate by demonstrating the superiority of CC3 (in terms of accuracy) compared to methods like CCSDT-3 or ADC(3). +This was further demonstrated in a recent study by two of the present authors \cite{Loos_2020d}. + %======================= \subsection{QUEST\#4} %======================= +The QUEST\#4 benchmark set \cite{Loos_2020c} consists of two subsets of excitations. +An ``exotic'' subset of 30 excited states for closed-shell molecules containing F, Cl, P, and Si atoms (carbonyl fluoride, \ce{CCl2}, \ce{CClF}, \ce{CF2}, difluorodiazirine, formyl fluoride, \ce{HCCl}, \ce{HCF}, \ce{HCP}, \ce{HPO}, \ce{HPS}, \ce{HSiF}, \ce{SiCl2}, and silylidene) and a ``radical'' subset of 51 doublet-doublet transitions in small radicals (allyl, \ce{BeF}, \ce{BeH}, \ce{BH2}, \ce{CH}, \ce{CH3}, \ce{CN}, \ce{CNO}, \ce{CON}, \ce{CO+}, \ce{F2BO}, \ce{F2BS}, \ce{H2BO}, \ce{HCO}, \ce{HOC}, \ce{H2PO}, \ce{H2PS}, \ce{NCO}, \ce{NH2}, nitromethyl, \ce{NO}, \ce{OH}, \ce{PH2}, and vinyl) characterized by open-shell electronic configurations and an unpaired electron. +This represents a total of 81 high-quality TBEs, the vast majority being obtained at the FCI level with at least the aug-cc-pVTZ basis set. +We further performed high-order CC calculations to ascertain these estimates. +For the exotic set, these TBEs have been used to assess the performances of 15 ``lower-order'' wave function approaches, including several CC and ADC variants. +Consistent with our previous works, we found that CC3 is very accurate, whereas the trends for the other methods are similar to that obtained on more standard organic compounds. +In contrast, for the radical set, even the refined ROCC3 method yields a MAE of $0.05$ eV. +Likewise, the excitation energies obtained with CCSD are much less satisfying for open-shell derivatives (MAE of $0.20$ eV with UCCSD and $0.15$ eV with ROCCSD) than for the closed-shell systems (MAE of $0.07$ eV). %======================= \subsection{QUEST\#5} %======================= +QUEST\#5 are additional accurate excitation energies that we have produced for the present article (aza-naphthalene, benzoquinone, cyclopentadienone, cyclopentadienethione, hexatriene, maleimide, naphthalene, nitroxyl, streptocyanine-C3, streptocyanine-C5, and thioacrolein). +The additional set is composed of small molecules as well as larger molecules. +QUEST\#5 does also provide additional FCI/6-31+G* estimates for the five- and six-membered rings considered in QUEST\#3. +\alert{add-on to other sets.} + %-------------------------------------- \subsubsection{Toward larger molecules} %-------------------------------------- +\alert{Here comes Denis' discussion of each new molecule.} + \begin{table}[bt] \centering \caption{Singlet and triplet excitation energies of various molecules obtained at the CC3, CCSDT, NEVPT2, and FCI levels of theory.} \begin{threeparttable} \begin{tabular}{lccrrr} \headrow + & & \mc{4}{c}{6-31+G*} \\ \thead{Molecule} & \thead{Transition} & \thead{CC3} & \thead{CCSDT} & \thead{NEVPT2} & \thead{FCI}\\ -Aza-naphthalene & & & & & \\ -Benzoquinone & & & & & \\ -Cyclopentadienone & & & & & \\ -Cyclopentadienethione & & & & & \\ -Hexatriene & & & & & \\ -Maleimide & & & & & \\ -Naphthalene & & & & & \\ -Nitroxyl & & & & & \\ -Streptocyanine-C3 & & & & & \\ -Streptocyanine-C5 & & & & & \\ -Thioacrolein & & & & & \\ +Aza-naphthalene + & $^1B_{3g}(n \ra \pis)$ \\ + & $^1B_{2u}(\pi \ra \pis)$ \\ + & $^1B_{1u}(n \ra \pis)$ \\ + & $^1B_{2g}(n \ra \pis)$ \\ + & $^1B_{2g}(n \ra \pis)$ \\ + & $^1B_{1u}(n \ra \pis)$ \\ + & $^1A_u(n \ra \pis)$ \\ + & $^1B_{3u}(\pi \ra \pis)$ \\ + & $^1A_g(\pi \ra \pis)$ \\ + & $^1A_u(n \ra \pis)$ \\ + & $^1A_g(n \ra 3s)$ \\ + & $^3B_{3g}(n \ra \pis)$ \\ + & $^3B_{2u}(\pi \ra \pis)$ \\ + & $^3B_{3u}(\pi \ra \pis)$ \\ + & $^3B_{1u}(n \ra \pis)$ \\ + & $^3B_{2g}(n \ra \pis)$ \\ + & $^3B_{2g}(n \ra \pis)$ \\ + & $^3B_{3u}(\pi \ra \pis)$ \\ + & $^3A_u(n \ra \pis)$ \\ +Benzoquinone + & $^1 B_{1g}(n \ra \pis)$ & & & & \\ + & $^1 A_{u}(n \ra \pis)$ & & & & \\ + & $^1 A_{g}(\double)$ & & & & \\ + & $^1 B_{3g}(\pi \ra \pis)$ & & & & \\ + & $^1 B_{3u}(n \ra \pis)$ & & & & \\ + & $^1 B_{2g}(n \ra \pis)$ & & & & \\ + & $^1 A_{u}(n \ra \pis)$ & & & & \\ + & $^1 B_{1g}(n \ra \pis)$ & & & & \\ + & $^1 B_{2g}(n \ra \pis)$ & & & & \\ + & $^3 B_{1g}(n \ra \pis)$ & & & & \\ + & $^3 A_{u}(n \ra \pis)$ & & & & \\ + & $^3 B_{1u}(\pi \ra \pis)$ & & & & \\ + & $^3 B_{3g}(\pi \ra \pis)$ & & & & \\ +Cyclopentadienone + & $^1A_2(n \ra \pis)$ \\ + & $^1B_2(\pi \ra \pis)$ \\ + & $^1B_1(\double)$ \\ + & $^1A_1(\double)$ \\ + & $^1A_1(\pi \ra \pis)$ \\ + & $^3B_2(\pi \ra \pis)$ \\ + & $^3A_2( \ra \pis)$ \\ + & $^3A_1(\pi \ra \pis)$ \\ + & $^3B_1(\double)$ \\ +Cyclopentadienethione + & $^1A_2(n \ra \pis)$ \\ + & $^1B_2(\pi \ra \pis)$ \\ + & $^1B_1(\double)$ \\ + & $^1A_1(\pi \ra \pis)$ \\ + & $^1A_1(\double)$ \\ + & $^3A_2(n \ra \pis)$ \\ + & $^3B_2(\pi \ra \pis)$ \\ + & $^3A_1(\pi \ra \pis)$ \\ + & $^3B_1(\double)$ \\ +Hexatriene + & $^1B_u(\pi \ra \pis)$ \\ + & $^1A_g(\pi \ra \pis)$ \\ + & $^1A_u(\pi \ra 3s)$ \\ + & $^1B_g(\pi \ra 3p)$ \\ + & $^3B_u(\pi \ra \pis)$ \\ + & $^3A_g(\pi \ra \pis)$ \\ +Maleimide + & $^1B_1(n \ra \pis)$ \\ + & $^1A_2(n \ra \pis)$ \\ + & $^1B_2 (\pi \ra \pis)$ \\ + & $^1B_2(\pi \ra \pis)$ \\ + & $^1B_2(n \ra 3s)$ \\ + & $^3B_1(n \ra \pis)$ \\ + & $^3B_2(\pi \ra \pis)$ \\ + & $^3B_2(\pi \ra \pis)$ \\ + & $^3A_2(n \ra \pis)$ \\ +Naphthalene + & $^1B_{3u}(\pi \ra \pis)$ \\ + & $^1B_{2u}(\pi \ra \pis)$ \\ + & $^1A_u(\pi \ra 3s)$ \\ + & $^1B_{1g}(\pi \ra \pis)$ \\ + & $^1A_g(\pi \ra \pis)$ \\ + & $^1B_{3g}(\pi \ra 3p)$ \\ + & $^1B_{2g}(\pi \ra 3p)$ \\ + & $^1B_{3u}(\pi \ra \pis)$ \\ + & $^1B_{1u}(\pi \ra 3s)$ \\ + & $^1B_{2u}(\pi \ra \pis)$ \\ + & $^1B_{1g}(\pi \ra \pis)$ \\ + & $^1A_g(\pi \ra \pis)$ \\ + & $^3B_{2u}(\pi \ra \pis)$ \\ + & $^3B_{3u}(\pi \ra \pis)$ \\ + & $^3B_{1g}(\pi \ra \pis)$ \\ + & $^3B_{2u}(\pi \ra \pis)$ \\ + & $^3B_{3u}(\pi \ra \pis)$ \\ + & $^3A_g(\pi \ra \pis)$ \\ + & $^3B_{1g}(\pi \ra \pis)$ \\ + & $^3A_g(\pi \ra \pis)$ \\ +Nitroxyl + & $^1A''(n \ra \pis)$ \\ + & $^1A'(\double)$ \\ + & $^1A'$ \\ + & $^3A''(n \ra \pis)$ \\ + & $^3A'(\pi \ra \pis)$ \\ +Streptocyanine-C3 + & $^1B_2(\pi \ra \pis)$ \\ + & $^3B_2(\pi \ra \pis)$ \\ +Streptocyanine-C5 + & $^1B_2(\pi \ra \pis)$ \\ + & $^3B_2(\pi \ra \pis)$ \\ +Thioacrolein + & $^1A''(n \ra \pis)$ \\ + & $^3A''(n \ra \pis)$ \\ %\hiderowcolors \hline % Please only put a hline at the end of the table \end{tabular} @@ -176,6 +390,8 @@ Thioacrolein & & & & & \\ \subsubsection{FCI excitation energies for five- and six-membered rings} %----------------------------------------------------------------------- +\alert{Here comes Anthony's new CIPSI numbers for the five- and six-membered rings.} + \begin{table}[bt] \centering \caption{Singlet and triplet excitation energies obtained at the CC3, CCSDT, and FCI levels of theory with the 6-31+G* basis set for various five- and six-membered rings.} @@ -219,26 +435,44 @@ Triazine & $^1A_1''(n \ra \pis)$ & 4.85 & 4.84 & 4.769(132) \\ %%%%%%%%%%%%%%%%%%%%%%%%%%%%% \section{Theoretical best estimates} +\label{sec:TBE} %%%%%%%%%%%%%%%%%%%%%%%%%%%%% + + +\begin{figure}[bt] + \centering + \includegraphics[width=0.5\linewidth]{example-image-rectangle} + \caption{This is the caption.} +\end{figure} + %%%%%%%%%%%%%%%%%%%%%%%%%%%%% \section{Benchmarks} +\label{sec:bench} %%%%%%%%%%%%%%%%%%%%%%%%%%%%% %%%%%%%%%%%%%%%%%%%%%%%%%%%%% \section{The QUESTDB website} +\label{sec:website} %%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\alert{Here comes the description of Mika's website.} + +%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\section{Concluding remarks} +\label{sec:ccl} +%%%%%%%%%%%%%%%%%%%%%%%%%%%%% %%%%%%%%%%%%%%%%%%%%%%%%%%%% -\section*{Acknowledgements} +\section*{acknowledgements} %%%%%%%%%%%%%%%%%%%%%%%%%%%% -PFL and AS thank the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Grant agreement No.~863481) for financial support. +This work was performed using HPC resources from GENCI-TGCC (Grand Challenge 2019-gch0418) and from CALMIP (Toulouse) under allocation 2020-18005. +AS, MC, and PFL thank the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Grant agreement No.~863481) for financial support. Funding from the \textit{``Centre National de la Recherche Scientifique''} is also acknowledged. DJ acknowledges the \textit{R\'egion des Pays de la Loire} for financial support. %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% -\section*{Conflict of interest} +\section*{conflict of interest} %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% The authors have declared no conflicts of interest for this article. @@ -264,6 +498,14 @@ In 2006, he obtained a Research Engineer position from the \textit{``Centre Nati \end{biography} %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\begin{biography}[example-image-1x1]{M.~Caffarel} +Please check with the journal's author guidelines whether author biographies are required. They are usually only included for review-type articles, and typically require photos and brief biographies (up to 75 words) for each author. +\bigskip +\bigskip +\end{biography} +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% + %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% \begin{biography}[example-image-1x1]{F.~Filippo} Please check with the journal's author guidelines whether author biographies are required. They are usually only included for review-type articles, and typically require photos and brief biographies (up to 75 words) for each author. @@ -280,14 +522,6 @@ Please check with the journal's author guidelines whether author biographies are \end{biography} %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% -%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% -\begin{biography}[DJacquemin]{D.~Jacquemin} -received his PhD in Chemistry from the University of Namur in 1998, before moving to the University of Florida for his postdoctoral stay. He is currently full Professor at the University of Nantes (France). -His research is focused on modeling electronically excited-state processes in organic and inorganic dyes as well as photochromes using a large panel of \emph{ab initio} approaches. His group collaborates with many experimental and theoretical groups. -He is the author of more than 500 scientific papers. He has been ERC grantee (2011--2016), member of Institut Universitaire de France (2012--2017) and received the WATOC's Dirac Medal (2014). -\end{biography} -%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% - %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% \begin{biography}[PFLoos]{P.-F.~Loos} received his his Ph.D.~in Computational and Theoretical Chemistry from the Universit\'e Henri Poincar\'e (Nancy, France) in 2008. @@ -297,6 +531,14 @@ Since 2017, he holds a researcher position from the \textit{``Centre National de \end{biography} %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% +\begin{biography}[DJacquemin]{D.~Jacquemin} +received his PhD in Chemistry from the University of Namur in 1998, before moving to the University of Florida for his postdoctoral stay. He is currently full Professor at the University of Nantes (France). +His research is focused on modeling electronically excited-state processes in organic and inorganic dyes as well as photochromes using a large panel of \emph{ab initio} approaches. His group collaborates with many experimental and theoretical groups. +He is the author of more than 500 scientific papers. He has been ERC grantee (2011--2016), member of Institut Universitaire de France (2012--2017) and received the WATOC's Dirac Medal (2014). +\end{biography} +%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% + \newpage \graphicalabstract{example-image-1x1}{Please check the journal's author guildines for whether a graphical abstract, key points, new findings, or other items are required for display in the Table of Contents.}