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%% This BibTeX bibliography file was created using BibDesk.
%% https://bibdesk.sourceforge.io/
%% Created for Pierre-Francois Loos at 2022-03-17 18:25:59 +0100
%% Created for Pierre-Francois Loos at 2022-03-17 21:43:00 +0100
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@article{Bittererova_2001,
author = {Bittererova, M and Brinck, T and Ostmark, H},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1016/S0009-2614(01)00454-7},
eissn = {1873-4448},
issn = {0009-2614},
journal = {Chem. Phys. Lett.},
month = {JUN 8},
number = {5-6},
orcid-numbers = {Brinck, Tore/0000-0003-2673-075X},
pages = {597-603},
researcherid-numbers = {Brinck, Tore/ABD-9838-2020},
title = {Theoretical study of the singlet electronically excited states of N-4},
unique-id = {WOS:000169373800030},
volume = {340},
year = {2001},
bdsk-url-1 = {https://doi.org/10.1016/S0009-2614(01)00454-7}}
@article{Bokarev_2009,
author = {Bokarev, Sergey I. and Dolgov, Evgeny K. and Bataev, Vadim A. and Godunov, Igor A.},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1002/qua.21838},
eissn = {1097-461X},
issn = {0020-7608},
journal = {Int. J. Quantum Chem.},
month = {MAR 5},
number = {3},
orcid-numbers = {Bokarev, Sergey I./0000-0003-0779-5013},
pages = {569-585},
researcherid-numbers = {Godunov, Igor/E-6082-2012 Bokarev, Sergey I./S-8682-2017 Godunov, Igor/H-8839-2012 Bataev, Vadim A/H-5671-2012},
title = {Molecular Parameters of Tetraatomic Carbonyls X2CO and XYCO (X, Y = H, F, Cl) in the Ground and Lowest Excited Electronic States, Part 1: A Test of Ab Initio Methods},
unique-id = {WOS:000262012700018},
volume = {109},
year = {2009},
bdsk-url-1 = {https://doi.org/10.1002/qua.21838}}
@article{Frankcombe_2011,
author = {Frankcombe, Terry J. and McNeil, Steven D. and Nyman, Gunnar},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1016/j.cplett.2011.08.047},
eissn = {1873-4448},
issn = {0009-2614},
journal = {Chem. Phys. Lett.},
month = {SEP 27},
number = {1-3},
pages = {40-43},
researcherid-numbers = {Nyman, Gunnar/B-1705-2009 Frankcombe, Terry/N-8329-2013},
title = {N plus CN -> C + N-2: A global potential energy surface, entrance channel recrossing and the applicability of capture theory},
unique-id = {WOS:000295537500008},
volume = {514},
year = {2011},
bdsk-url-1 = {https://doi.org/10.1016/j.cplett.2011.08.047}}
@article{Gu_2008,
author = {Gu, Junjing and Lin, Yonghui and Ma, Ben and Wu, Wei and Shaik, Sason},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1021/ct800341z},
eissn = {1549-9626},
issn = {1549-9618},
journal = {J. Chem. Theory Comput.},
month = {DEC},
number = {12},
pages = {2101-2107},
researcherid-numbers = {Wu, Wei/G-4595-2010},
title = {Covalent Excited States of Polyenes C2nH2n+2 (n=2-8) and Polyenyl Radicals C2n-1H2n+1 (n=2-8): An Ab Initio Valence Bond Study},
unique-id = {WOS:000261613800012},
volume = {4},
year = {2008},
bdsk-url-1 = {https://doi.org/10.1021/ct800341z}}
@article{Kerkines_2005,
author = {Kerkines, ISK and Carsky, P and Mavridis, A},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1021/jp054530z},
issn = {1089-5639},
journal = {J. Phys. Chem. A},
month = {NOV 10},
number = {44},
orcid-numbers = {Kerkines, Ioannis/0000-0002-9483-8327 MAVRIDIS, ARISTIDES/0000-0003-1342-696X},
pages = {10148-10152},
researcherid-numbers = {Mavridis, Aristides/AAF-4460-2019 Carsky, Petr/F-6090-2014},
title = {A multireference coupled-cluster potential energy surface of diazomethane, CH2N2},
unique-id = {WOS:000233342300029},
volume = {109},
year = {2005},
bdsk-url-1 = {https://doi.org/10.1021/jp054530z}}
@article{Lampart_2008,
author = {Lampart, W. M. and Schofield, D. P. and Christie, R. A. and Jordan, K. D.},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1080/00268970802317504},
eissn = {1362-3028},
issn = {0026-8976},
journal = {Mol. Phys.},
number = {12-13},
orcid-numbers = {Christie, Richard/0000-0001-8603-5834},
pages = {1697-1702},
researcherid-numbers = {Christie, Richard/E-5144-2015},
title = {Model systems for exploring electron correlation effects in the buckling of SiSi dimers on the Si(100) surface},
unique-id = {WOS:000259225800024},
volume = {106},
year = {2008},
bdsk-url-1 = {https://doi.org/10.1080/00268970802317504}}
@article{Leininger_2000,
author = {Leininger, T and Gadea, FX},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1088/0953-4075/33/4/311},
issn = {0953-4075},
journal = {J. Phys. B At. Mol. Opt .},
month = {FEB 28},
number = {4},
pages = {735-744},
title = {Ab initio calculations for electron attachment to Cl-2},
unique-id = {WOS:000085813400017},
volume = {33},
year = {2000},
bdsk-url-1 = {https://doi.org/10.1088/0953-4075/33/4/311}}
@article{Maranzana_2020,
author = {Maranzana, Andrea and Tonachini, Glauco},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1021/acs.jpca.9b11430},
eissn = {1520-5215},
issn = {1089-5639},
journal = {J. Phys. Chem. A},
month = {FEB 13},
number = {6, SI},
orcid-numbers = {TONACHINI, Glauco/0000-0001-7845-1475},
pages = {1112-1120},
title = {Multireference Study of the H2COO (Criegee Intermediate) + O-3 Addition: A Reaction of Possible Tropospheric Interest},
unique-id = {WOS:000514222100008},
volume = {124},
year = {2020},
bdsk-url-1 = {https://doi.org/10.1021/acs.jpca.9b11430}}
@article{Papakondylis_1999,
author = {Papakondylis, A and Mavridis, A},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1021/jp983403i},
issn = {1089-5639},
journal = {J. Phys. Chem. A},
month = {MAR 4},
number = {9},
orcid-numbers = {Papakondylis, Aristotle/0000-0003-1534-2380 MAVRIDIS, ARISTIDES/0000-0003-1342-696X},
pages = {1255-1259},
researcherid-numbers = {Papakondylis, Aristotle/AAF-3542-2019 Mavridis, Aristides/AAF-4460-2019},
title = {A theoretical investigation of the structure and bonding of diazomethane, CH2N2},
unique-id = {WOS:000079150000012},
volume = {103},
year = {1999},
bdsk-url-1 = {https://doi.org/10.1021/jp983403i}}
@article{Schild_2013,
author = {Schild, Axel and Paulus, Beate},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1002/jcc.23273},
eissn = {1096-987X},
issn = {0192-8651},
journal = {J. Comput. Chem.},
month = {JUN 15},
number = {16},
orcid-numbers = {Schild, Axel/0000-0002-0852-0938},
pages = {1393-1397},
title = {Multireference calculations for ring inversion and double bond shifting in cyclooctatetraene},
unique-id = {WOS:000318696800004},
volume = {34},
year = {2013},
bdsk-url-1 = {https://doi.org/10.1002/jcc.23273}}
@article{Sun_2018,
author = {Sun, Zhi and Schaefer, III, Henry F.},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1039/c8cp03434f},
eissn = {1463-9084},
issn = {1463-9076},
journal = {Phys. Chem. Chem. Phys.},
month = {JUL 28},
number = {28},
orcid-numbers = {Sun, Zhi/0000-0001-8333-7976},
pages = {18986-18994},
title = {Vibrational frequencies, structures, and energetics of the highly challenging alkali metal trifluorides MF3 (M = Li, Na, K, Rb, and Cs)},
unique-id = {WOS:000439286000011},
volume = {20},
year = {2018},
bdsk-url-1 = {https://doi.org/10.1039/c8cp03434f}}
@article{Takatani_2009,
author = {Takatani, Tait and Sears, John S. and Sherrill, C. David},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1021/jp903865t},
issn = {1089-5639},
journal = {J. Phys. Chem. A},
month = {AUG 13},
number = {32},
orcid-numbers = {Sherrill, David/0000-0002-5570-7666},
pages = {9231-9236},
title = {Assessing the Performance of Density Functional Theory for the Electronic Structure of Metal-Salens: The d(6)-Metals},
unique-id = {WOS:000268660900024},
volume = {113},
year = {2009},
bdsk-url-1 = {https://doi.org/10.1021/jp903865t}}
@article{Takatani_2010,
author = {Takatani, Tait and Sears, John S. and Sherrill, C. David},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1021/jp1046084},
issn = {1089-5639},
journal = {J. Phys. Chem. A},
month = {NOV 4},
number = {43},
orcid-numbers = {Sherrill, David/0000-0002-5570-7666},
pages = {11714-11718},
title = {Assessing the Performance of Density Functional Theory For the Electronic Structure of Metal-Salens: The M06 Suite of Functionals and the d(4)-Metals},
unique-id = {WOS:000283471900041},
volume = {114},
year = {2010},
bdsk-url-1 = {https://doi.org/10.1021/jp1046084}}
@article{Verma_2018,
author = {Verma, Pragya and Varga, Zoltan and Truhlar, Donald G.},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1021/acs.jpca.7b12652},
eissn = {1520-5215},
issn = {1089-5639},
journal = {J. Phys. Chem. A},
month = {MAR 8},
number = {9},
orcid-numbers = {Verma, Pragya/0000-0002-5722-0894 Varga, Zolt{\'a}n/0000-0002-9324-798X Truhlar, Donald G./0000-0002-7742-7294 Varga, Zolt{\'a}n/0000-0002-9324-798X Kundu, Achintya/0000-0002-6252-1763 CHO, MINHAENG/0000-0003-1618-1056},
pages = {2563-2579},
researcherid-numbers = {Verma, Pragya/B-5090-2018 Varga, Zolt{\'a}n/H-9937-2014 Truhlar, Donald G./G-7076-2015 Varga, Zolt{\'a}n/N-7454-2019 Kundu, Achintya/D-4910-2018 CHO, MINHAENG/C-9983-2011},
title = {Hyper Open-Shell Excited Spin States of Transition-Metal Compounds: FeF2, FeF2 center dot center dot center dot Ethane, and FeF2 center dot center dot center dot Ethylene},
unique-id = {WOS:000427331100023},
volume = {122},
year = {2018},
bdsk-url-1 = {https://doi.org/10.1021/acs.jpca.7b12652}}
@article{Woywod_2010,
author = {Woywod, Clemens and Papp, Attila and Halasz, Gabor J. and Vibok, Agnes},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1007/s00214-009-0678-x},
eissn = {1432-2234},
issn = {1432-881X},
journal = {Theor. Chem. Acc.},
month = {MAR},
number = {3-6},
orcid-numbers = {woywod, clemens/0000-0002-3407-1486},
pages = {521-533},
researcherid-numbers = {woywod, clemens/Q-2939-2017},
title = {Theoretical investigation of the electronic spectrum of pyrazine},
unique-id = {WOS:000273363300039},
volume = {125},
year = {2010},
bdsk-url-1 = {https://doi.org/10.1007/s00214-009-0678-x}}
@article{Yan_2004,
author = {Yan, TY and Hase, WL and Doubleday, C},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1063/1.1705574},
eissn = {1089-7690},
issn = {0021-9606},
journal = {J. Chem. Phys.},
month = {MAY 15},
number = {19},
orcid-numbers = {Hase, William/0000-0002-0560-5100},
pages = {9253-9265},
title = {Energetics, transition states, and intrinsic reaction coordinates for reactions associated with O(P-3) processing of hydrocarbon materials},
unique-id = {WOS:000221146400040},
volume = {120},
year = {2004},
bdsk-url-1 = {https://doi.org/10.1063/1.1705574}}
@article{Zhang_2020,
author = {Zhang, Dayou and Truhlar, Donald G.},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1021/acs.jctc.0c00518},
eissn = {1549-9626},
issn = {1549-9618},
journal = {J. Chem. Theory Comput.},
month = {JUL 14},
number = {7},
orcid-numbers = {Zhang, Dayou/0000-0002-5393-657X Truhlar, Donald G./0000-0002-7742-7294},
pages = {4416-4428},
researcherid-numbers = {Zhang, Dayou/AAS-2448-2020 Truhlar, Donald G./G-7076-2015},
title = {Spin Splitting Energy of Transition Metals: A New, More Affordable Wave Function Benchmark Method and Its Use to Test Density Functional Theory},
unique-id = {WOS:000607532300036},
volume = {16},
year = {2020},
bdsk-url-1 = {https://doi.org/10.1021/acs.jctc.0c00518}}
@article{Zhu_2005,
author = {Zhu, RS and Lin, MC},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1002/kin.20066},
eissn = {1097-4601},
issn = {0538-8066},
journal = {Int. J. Quantum Chem.},
month = {OCT},
number = {10},
pages = {593-598},
title = {Ab initio study of the oxidation of NCN by O-2},
unique-id = {WOS:000232007900002},
volume = {37},
year = {2005},
bdsk-url-1 = {https://doi.org/10.1002/kin.20066}}
@article{Zhu_2007,
author = {Zhu, R. S. and Lin, M. C.},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1021/jp068991b},
issn = {1089-5639},
journal = {J. Phys. Chem. A},
month = {JUL 26},
number = {29},
pages = {6766-6771},
title = {Ab initio study on the oxidation of NCN by O (P-3): Prediction of the total rate constant and product branching ratios},
unique-id = {WOS:000248121400024},
volume = {111},
year = {2007},
bdsk-url-1 = {https://doi.org/10.1021/jp068991b}}
@article{Zhu_2013,
author = {Zhu, R. S. and Raghunath, P. and Lin, M. C.},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1021/jp401148q},
issn = {1089-5639},
journal = {J. Phys. Chem. A},
month = {AUG 15},
number = {32},
pages = {7308-7313},
title = {Effect of Roaming Transition States upon Product Branching in the Thermal Decomposition of CH3NO2},
unique-id = {WOS:000323300800041},
volume = {117},
year = {2013},
bdsk-url-1 = {https://doi.org/10.1021/jp401148q}}
@article{Zou_2009,
author = {Zou, Wenli and Liu, Wenjian},
date-added = {2022-03-17 21:11:59 +0100},
date-modified = {2022-03-17 21:11:59 +0100},
doi = {10.1002/jcc.21080},
issn = {0192-8651},
journal = {J. Comput. Chem.},
month = {MAR},
number = {4},
orcid-numbers = {Liu, Wenjian/0000-0002-1630-3466 Liu, Wenjian/0000-0002-1630-3466},
pages = {524-539},
researcherid-numbers = {Liu, Wenjian/N-7575-2016 Liu, Wenjian/M-4234-2019},
title = {Comprehensive Ab Initio Calculation and Simulation on the Low-Lying Electronic States of TlX (X = F, Cl, Br, I, and At)},
unique-id = {WOS:000263315800003},
volume = {30},
year = {2009},
bdsk-url-1 = {https://doi.org/10.1002/jcc.21080}}
@article{Li_2021,
author = {Li,Chenyang and Evangelista,Francesco A.},
date-added = {2022-03-17 18:25:45 +0100},
@ -117,14 +491,12 @@
@article{Wen_2018,
author = {Wen, Jin and Han, Bowen and Havlas, Zden{\v e}k and Michl, Josef},
date-added = {2022-03-17 17:14:20 +0100},
date-modified = {2022-03-17 17:14:26 +0100},
date-modified = {2022-03-17 21:42:21 +0100},
doi = {10.1021/acs.jctc.8b00136},
eprint = {https://doi.org/10.1021/acs.jctc.8b00136},
journal = {J. Chem. Theory Comput.},
number = {8},
pages = {4291--4297},
title = {An MS-CASPT2 Calculation of the Excited Electronic States of an Axial Difluoroborondipyrromethene (BODIPY) Dimer},
url = {https://doi.org/10.1021/acs.jctc.8b00136},
volume = {14},
year = {2018},
bdsk-url-1 = {https://doi.org/10.1021/acs.jctc.8b00136}}
@ -133,15 +505,12 @@
abstract = {Complete active space self-consistent field theory (CASSCF) calculations and subsequent second-order perturbation theory treatment (CASPT2) are discussed in the evaluation of the spin-states energy difference (ΔHelec) of a series of seven spin crossover (SCO) compounds. The reference values have been extracted from a combination of experimental measurements and DFT + U calculations, as discussed in a recent article (Vela et al., Phys Chem Chem Phys 2015, 17, 16306). It is definitely proven that the critical IPEA parameter used in CASPT2 calculations of ΔHelec, a key parameter in the design of SCO compounds, should be modified with respect to its default value of 0.25 a.u. and increased up to 0.50 a.u. The satisfactory agreement observed previously in the literature might result from an error cancellation originated in the default IPEA, which overestimates the stability of the HS state, and the erroneous atomic orbital basis set contraction of carbon atoms, which stabilizes the LS states. {\copyright} 2015 Wiley Periodicals, Inc.},
author = {Vela, Sergi and Fumanal, Maria and Ribas-Ari{\~n}o, Jordi and Robert, Vincent},
date-added = {2022-03-17 17:14:06 +0100},
date-modified = {2022-03-17 17:14:12 +0100},
date-modified = {2022-03-17 21:42:09 +0100},
doi = {https://doi.org/10.1002/jcc.24283},
eprint = {https://onlinelibrary.wiley.com/doi/pdf/10.1002/jcc.24283},
journal = {J. Comput. Chem.},
keywords = {spin crossover, molecular magnetism, computational chemistry},
number = {10},
pages = {947--953},
title = {On the Zeroth-Order Hamiltonian for CASPT2 Calculations of Spin Crossover Compounds},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/jcc.24283},
volume = {37},
year = {2016},
bdsk-url-1 = {https://onlinelibrary.wiley.com/doi/abs/10.1002/jcc.24283},
@ -150,14 +519,12 @@
@article{Rudavskyi_2014,
author = {Rudavskyi,Andrii and Sousa,Carmen and de Graaf,Coen and Havenith,Remco W. A. and Broer,Ria},
date-added = {2022-03-17 17:13:51 +0100},
date-modified = {2022-03-17 17:14:05 +0100},
date-modified = {2022-03-17 21:41:57 +0100},
doi = {10.1063/1.4875695},
eprint = {https://doi.org/10.1063/1.4875695},
journal = {J. Chem. Phys.},
number = {18},
pages = {184318},
title = {Computational Approach to the Study of Thermal Spin Crossover Phenomena},
url = {https://doi.org/10.1063/1.4875695},
volume = {140},
year = {2014},
bdsk-url-1 = {https://doi.org/10.1063/1.4875695}}
@ -165,14 +532,12 @@
@article{Daku_2012,
author = {Lawson Daku, Lat{\'e}vi Max and Aquilante, Francesco and Robinson, Timothy W. and Hauser, Andreas},
date-added = {2022-03-17 17:13:29 +0100},
date-modified = {2022-03-17 17:13:42 +0100},
date-modified = {2022-03-17 21:41:44 +0100},
doi = {10.1021/ct300592w},
eprint = {https://doi.org/10.1021/ct300592w},
journal = {J. Chem. Theory Comput.},
number = {11},
pages = {4216--4231},
title = {Accurate Spin-State Energetics of Transition Metal Complexes. 1. CCSD(T), CASPT2, and DFT Study of [M(NCH)$_6$]$^{2+}$ (M = Fe, Co)},
url = {https://doi.org/10.1021/ct300592w},
volume = {8},
year = {2012},
bdsk-url-1 = {https://doi.org/10.1021/ct300592w}}
@ -180,14 +545,12 @@
@article{Kepenekian_2009,
author = {Kepenekian,Mika{\"e}l and Robert,Vincent and Le Guennic,Boris},
date-added = {2022-03-17 17:13:14 +0100},
date-modified = {2022-03-17 17:13:29 +0100},
date-modified = {2022-03-17 21:41:24 +0100},
doi = {10.1063/1.3211020},
eprint = {https://doi.org/10.1063/1.3211020},
journal = {J. Chem. Phys.},
number = {11},
pages = {114702},
title = {What Zeroth-Order Hamiltonian for CASPT2 Adiabatic Energetics of Fe(II)N$_6$ Architectures?},
url = {https://doi.org/10.1063/1.3211020},
volume = {131},
year = {2009},
bdsk-url-1 = {https://doi.org/10.1063/1.3211020}}
@ -195,14 +558,12 @@
@article{Suaud_2009,
author = {Suaud, Nicolas and Bonnet, Marie-Laure and Boilleau, Corentin and Lab{\`e}guerie, Pierre and Guih{\'e}ry, Nathalie},
date-added = {2022-03-17 17:12:58 +0100},
date-modified = {2022-03-17 17:13:05 +0100},
date-modified = {2022-03-17 21:41:06 +0100},
doi = {10.1021/ja805626s},
eprint = {https://doi.org/10.1021/ja805626s},
journal = {J. Am. Chem. Soc.},
number = {2},
pages = {715-722},
title = {Light-Induced Excited Spin State Trapping: Ab Initio Study of the Physics at the Molecular Level},
url = {https://doi.org/10.1021/ja805626s},
volume = {131},
year = {2009},
bdsk-url-1 = {https://doi.org/10.1021/ja805626s}}
@ -210,14 +571,12 @@
@article{Pierloot_2008,
author = {Pierloot,Kristine and Vancoillie,Steven},
date-added = {2022-03-17 17:12:41 +0100},
date-modified = {2022-03-17 17:12:47 +0100},
date-modified = {2022-03-17 21:40:53 +0100},
doi = {10.1063/1.2820786},
eprint = {https://doi.org/10.1063/1.2820786},
journal = {J. Chem. Phys.},
number = {3},
pages = {034104},
title = {Relative Energy of the High-($^5T_{2g}$) and Low-($^1A_{1g}$) Spin states of the Ferrous Complexes [Fe(L)(NHS$_4$)]: CASPT2 versus Density Functional Theory},
url = {https://doi.org/10.1063/1.2820786},
volume = {128},
year = {2008},
bdsk-url-1 = {https://doi.org/10.1063/1.2820786}}
@ -225,14 +584,12 @@
@article{Pierloot_2006,
author = {Pierloot,Kristine and Vancoillie,Steven},
date-added = {2022-03-17 17:12:20 +0100},
date-modified = {2022-03-17 17:12:34 +0100},
date-modified = {2022-03-17 21:40:48 +0100},
doi = {10.1063/1.2353829},
eprint = {https://doi.org/10.1063/1.2353829},
journal = {J. Chem. Phys.},
number = {12},
pages = {124303},
title = {Relative Energy of the High-($^5T_{2g}$) and low-($^1A_{1g}$) Spin States of [Fe(H$_2$O)$_6$]$^{2+}$, [Fe(NH$_3$)$_6$]$^{2+}$, and [Fe(bpy)$_3$]$^{2+}$: CASPT2 \emph{versus} Density Functional Theory},
url = {https://doi.org/10.1063/1.2353829},
volume = {125},
year = {2006},
bdsk-url-1 = {https://doi.org/10.1063/1.2353829}}
@ -303,15 +660,12 @@
abstract = {The present contribution contains an overview of quantum-chemical methods and strategies to compute and interpret spectroscopic and photochemical phenomena in molecular systems. The state of the art for the quantum chemistry of the excited state is reviewed, focusing in the advantages and disadvantages of the most commonly employed computational methods, from the single configurational procedures like CI-Singles (CIS), propagator approaches, and Coupled-Cluster (CC) techniques, to the more sophisticated multiconfigurational treatments, with particular emphasis on perturbation theory, the CASPT2 approach. Also, a short summary on the performance, lights, and shadows of the popular TDDFT methods is included. The role of the differential correlation effects on quantum-chemical calculations is analyzed, especially for the location of potential energy surface crossings. The contribution finally addresses the importance that theoretical constructs as conical and non-conical intersections play in non-adiabatic photochemistry. The nice photochemistry of cytosine is used as an illustrative example of theoretical photochemistry, a continuously expanding field of research.},
author = {Luis Serrano-Andr\'{e}s and Manuela Merch\'{a}n},
date-added = {2022-03-17 15:17:55 +0100},
date-modified = {2022-03-17 15:18:04 +0100},
date-modified = {2022-03-17 21:40:26 +0100},
doi = {https://doi.org/10.1016/j.theochem.2005.03.020},
issn = {0166-1280},
journal = {J. Mol. Struct. (THEOCHEM)},
keywords = {Excited states, Photochemistry, Quantum chemistry},
number = {1},
pages = {99--108},
title = {Quantum Chemistry of the Excited State: 2005 Overview},
url = {http://www.sciencedirect.com/science/article/pii/S0166128005002460},
volume = {729},
year = {2005},
bdsk-url-1 = {http://www.sciencedirect.com/science/article/pii/S0166128005002460},
@ -320,14 +674,12 @@
@article{Serrano-Andres_2002,
author = {Serrano-Andr{\'e}s,Luis and Pou-Am{\'e}rigo,Rosendo and F{\"u}lscher,Markus P. and Borin,Antonio Carlos},
date-added = {2022-03-17 15:17:40 +0100},
date-modified = {2022-03-17 15:17:48 +0100},
date-modified = {2022-03-17 21:40:15 +0100},
doi = {10.1063/1.1482706},
eprint = {https://doi.org/10.1063/1.1482706},
journal = {J. Chem. Phys.},
number = {4},
pages = {1649--1659},
title = {Electronic Excited States of Conjugated Cyclic Ketones and Thioketones: A Theoretical Study},
url = {https://doi.org/10.1063/1.1482706},
volume = {117},
year = {2002},
bdsk-url-1 = {https://doi.org/10.1063/1.1482706}}
@ -335,14 +687,12 @@
@article{Roos_2002,
author = {Bj{\"o}rn O. Roos and Per-{\AA}ke Malmqvist and Vincent Molina and Luis Serrano-Andr{\'e}s and Manuela Merch{\'a}n},
date-added = {2022-03-17 15:17:24 +0100},
date-modified = {2022-03-17 15:17:32 +0100},
date-modified = {2022-03-17 21:40:01 +0100},
doi = {10.1063/1.1465406},
eprint = {https://doi.org/10.1063/1.1465406},
journal = {J. Chem. Phys.},
number = {17},
pages = {7526--7536},
title = {Theoretical Characterization of the Lowest-Energy Absorption Band of Pyrrole},
url = {https://doi.org/10.1063/1.1465406},
volume = {116},
year = {2002},
bdsk-url-1 = {https://doi.org/10.1063/1.1465406},
@ -366,14 +716,12 @@
@article{Roos_1999,
author = {Roos, Bj{\"o}rn O.},
date-added = {2022-03-17 15:15:58 +0100},
date-modified = {2022-03-17 15:16:04 +0100},
date-modified = {2022-03-17 21:39:51 +0100},
doi = {10.1021/ar960091y},
eprint = {https://doi.org/10.1021/ar960091y},
journal = {Acc. Chem. Res.},
number = {2},
pages = {137--144},
title = {Theoretical Studies of Electronically Excited States of Molecular Systems Using Multiconfigurational Perturbation Theory},
url = {https://doi.org/10.1021/ar960091y},
volume = {32},
year = {1999},
bdsk-url-1 = {https://doi.org/10.1021/ar960091y}}
@ -381,14 +729,12 @@
@article{Serrano-Andres_1998a,
author = {Serrano-Andr{\'e}s,Luis and Forsberg,Niclas and Malmqvist,Per-{\AA}ke},
date-added = {2022-03-17 15:15:30 +0100},
date-modified = {2022-03-17 15:15:45 +0100},
date-modified = {2022-03-17 21:39:33 +0100},
doi = {10.1063/1.476138},
eprint = {https://doi.org/10.1063/1.476138},
journal = {J. Chem. Phys.},
number = {17},
pages = {7202--7216},
title = {Vibronic Structure in Triatomic Molecules: The Hydrocarbon Flame Bands of the Formyl Radical (HCO). A Theoretical Study},
url = {https://doi.org/10.1063/1.476138},
volume = {108},
year = {1998},
bdsk-url-1 = {https://doi.org/10.1063/1.476138}}
@ -396,14 +742,12 @@
@article{Serrano-Andres_1998b,
author = {Serrano-Andr{\'e}s, Luis and F{\"u}lscher, Markus P.},
date-added = {2022-03-17 15:15:30 +0100},
date-modified = {2022-03-17 15:15:42 +0100},
date-modified = {2022-03-17 21:39:36 +0100},
doi = {10.1021/ja981148+},
eprint = {https://doi.org/10.1021/ja981148+},
journal = {J. Am. Chem. Soc.},
number = {42},
pages = {10912--10920},
title = {Theoretical Study of the Electronic Spectroscopy of Peptides. III. Charge-Transfer Transitions in Polypeptides},
url = {https://doi.org/10.1021/ja981148+},
volume = {120},
year = {1998},
bdsk-url-1 = {https://doi.org/10.1021/ja981148+}}
@ -411,14 +755,12 @@
@article{Serrano-Andres_1996a,
author = {Serrano-Andr{\'e}s, Luis and F{\"u}lscher, Markus P.},
date-added = {2022-03-17 15:15:08 +0100},
date-modified = {2022-03-17 15:15:19 +0100},
date-modified = {2022-03-17 21:39:19 +0100},
doi = {10.1021/ja961996+},
eprint = {https://doi.org/10.1021/ja961996+},
journal = {J. Am. Chem. Soc.},
number = {48},
pages = {12190--12199},
title = {Theoretical Study of the Electronic Spectroscopy of Peptides. 1. The Peptidic Bond: Primary, Secondary, and Tertiary Amides},
url = {https://doi.org/10.1021/ja961996+},
volume = {118},
year = {1996},
bdsk-url-1 = {https://doi.org/10.1021/ja961996+}}
@ -426,14 +768,12 @@
@article{Serrano-Andres_1996b,
author = {Serrano-Andr{\'e}s, Luis and F{\"u}lscher, Markus P. and Roos, Bj{\"o}rn O. and Merch{\'a}n, Manuela},
date-added = {2022-03-17 15:15:08 +0100},
date-modified = {2022-03-17 15:15:17 +0100},
date-modified = {2022-03-17 21:39:22 +0100},
doi = {10.1021/jp952809h},
eprint = {https://doi.org/10.1021/jp952809h},
journal = {J. Phys. Chem.},
number = {16},
pages = {6484--6491},
title = {Theoretical Study of the Electronic Spectrum of Imidazole},
url = {https://doi.org/10.1021/jp952809h},
volume = {100},
year = {1996},
bdsk-url-1 = {https://doi.org/10.1021/jp952809h}}
@ -441,14 +781,12 @@
@article{Serrano-Andres_1995,
author = {Serrano-Andres, Luis and Merchan, Manuela and Roos, Bjoern O. and Lindh, Roland},
date-added = {2022-03-17 15:14:20 +0100},
date-modified = {2022-03-17 15:14:29 +0100},
date-modified = {2022-03-17 21:39:06 +0100},
doi = {10.1021/ja00116a024},
eprint = {https://doi.org/10.1021/ja00116a024},
journal = {J. Am. Chem. Soc.},
number = {11},
pages = {3189--3204},
title = {Theoretical Study of the Internal Charge Transfer in Aminobenzonitriles},
url = {https://doi.org/10.1021/ja00116a024},
volume = {117},
year = {1995},
bdsk-url-1 = {https://doi.org/10.1021/ja00116a024}}
@ -466,14 +804,12 @@
@article{Serrano-Andres_1993b,
author = {Serrano-Andr\'es, Luis and Merch\'{a}n, Manuela and Nebot-Gil, Ignacio and Roos, Bjoern O. and Fulscher, Markus},
date-added = {2022-03-17 15:13:13 +0100},
date-modified = {2022-03-17 15:13:49 +0100},
date-modified = {2022-03-17 21:38:52 +0100},
doi = {10.1021/ja00067a038},
eprint = {https://doi.org/10.1021/ja00067a038},
journal = {J. Am. Chem. Soc.},
number = {14},
pages = {6184--6197},
title = {Theoretical Study of the Electronic Spectra of Cyclopentadiene, Pyrrole, and Furan},
url = {https://doi.org/10.1021/ja00067a038},
volume = {115},
year = {1993},
bdsk-url-1 = {https://doi.org/10.1021/ja00067a038}}
@ -482,14 +818,12 @@
abstract = {The electronic spectrum of thiophene has been studied using multiconfiguration second-order perturbation theory and extended ANO basis sets. The calculations comprise four singlet valence excited states and the 3s3p3rd Rydberg series. The lowest triplet states were included and some n-π* and n-σ* states. The results have been used to assign the experimental spectrum below 8.0 eV, with a maximum deviation of about 0.1 eV for vertical transition energies. The calculations place the 2 1A1 valence state at 5.33 eV, below the 1 1B2 valence state at 5.72 eV, and the most intense valence transitions at 6.69 eV (3 1A1) and 7.32 eV (4 1B2) with oscillator strengths 0.19 and 0.39, respectively.},
author = {Luis Serrano-Andr{\'e}s and Manuela Merch{\'a}n and Markus F{\"u}lscher and Bj{\"o}rn O. Roos},
date-added = {2022-03-17 15:13:13 +0100},
date-modified = {2022-03-17 15:13:54 +0100},
date-modified = {2022-03-17 21:38:57 +0100},
doi = {https://doi.org/10.1016/0009-2614(93)80061-S},
issn = {0009-2614},
journal = {Chem. Phys. Lett.},
number = {1},
pages = {125--134},
title = {A Theoretical Study of the Electronic Spectrum of Thiophene},
url = {http://www.sciencedirect.com/science/article/pii/000926149380061S},
volume = {211},
year = {1993},
bdsk-url-1 = {http://www.sciencedirect.com/science/article/pii/000926149380061S},
@ -1127,10 +1461,10 @@
year = {2021},
bdsk-url-1 = {https://doi.org/10.1063/5.0065314}}
@article{Leininger_2000,
@article{Leininger_2000a,
author = {Leininger,Matthew L. and Allen,Wesley D. and Schaefer,Henry F. and Sherrill,C. David},
date-added = {2022-03-16 09:02:59 +0100},
date-modified = {2022-03-16 09:02:59 +0100},
date-modified = {2022-03-17 21:12:15 +0100},
doi = {10.1063/1.481764},
journal = {J. Chem. Phys.},
number = {21},
@ -3354,19 +3688,6 @@
year = {2003},
bdsk-url-1 = {https://doi.org/10.1080/0026897031000082149}}
@article{Zhang_2020,
author = {Zhang, Ning and Liu, Wenjian and Hoffmann, Mark R.},
date-added = {2020-10-09 12:06:01 +0200},
date-modified = {2020-10-09 12:06:54 +0200},
doi = {10.1021/acs.jctc.9b01200},
journal = {J. Chem. Theory Comput.},
number = {4},
pages = {2296-2316},
title = {Iterative Configuration Interaction with Selection},
volume = {16},
year = {2020},
bdsk-url-1 = {https://doi.org/10.1021/acs.jctc.9b01200}}
@article{Lei_2017,
author = {Yibo Lei and Wenjian Liu and Mark R. Hoffmann},
date-added = {2020-10-09 12:04:45 +0200},

41
Manuscript/CASPT3.tex
View File

@ -84,8 +84,8 @@
% Abstract
\begin{abstract}
The present study assesses the performance of the third-order multireference perturbation theory, CASPT3, in the context of molecular excited states.
Based on 284 vertical excitation energies of various natures extracted from the QUEST database, we show that CASPT3 provides a significant improvement compared to its second-order counterpart, CASPT2.
The present study assesses the accuracy of third-order multireference perturbation theory, CASPT3, in the context of molecular excited states.
Based on 284 vertical transition energies of various natures extracted from the QUEST database, we show that CASPT3 provides a significant improvement compared to its second-order counterpart, CASPT2.
As already reported, we have also observed that the accuracy of CASPT3 is much less sensitive to the infamous ionization-potential-electron-affinity (IPEA) shift.
%\bigskip
%\begin{center}
@ -103,9 +103,9 @@ As already reported, we have also observed that the accuracy of CASPT3 is much l
\label{sec:intro}
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
Perturbation theory is a relatively inexpensive and size-extensive route towards the exact solution of the Schr\"odinger equation.
Perturbation theory is a relatively inexpensive route towards the exact solution of the Schr\"odinger equation.
However, it rarely works this way in practice as the perturbative series may exhibit quite a large spectrum of behaviors. \cite{Olsen_1996,Christiansen_1996,Cremer_1996,Olsen_2000,Olsen_2019,Stillinger_2000,Goodson_2000a,Goodson_2000b,Goodson_2004,Sergeev_2005,Sergeev_2006,Goodson_2011}
For example, in single-reference M{\o}ller-Plesset (MP) perturbation theory, \cite{Moller_1934} erratic, slowly convergent, and divergent behaviors have been observed. \cite{Laidig_1985,Knowles_1985,Handy_1985,Gill_1986,Laidig_1987,Nobes_1987,Gill_1988,Gill_1988a,Lepetit_1988,Leininger_2000,Malrieu_2003,Damour_2021}
For example, in single-reference M{\o}ller-Plesset (MP) perturbation theory, \cite{Moller_1934} erratic, slowly convergent, and divergent behaviors have been observed. \cite{Laidig_1985,Knowles_1985,Handy_1985,Gill_1986,Laidig_1987,Nobes_1987,Gill_1988,Gill_1988a,Lepetit_1988,Leininger_2000a,Malrieu_2003,Damour_2021}
Systematic improvement is thus difficult to achieve and it is extremely challenging to predict, \textit{a priori}, the behavior of the series. \cite{Marie_2021a}
This has led, in certain specific contexts, to the development of empirical strategy like MP2.5 where one simply averages the second-order (MP2) and third-order (MP3) total energies. \cite{Pitonak_2009}
@ -114,10 +114,10 @@ construction (ADC) approximation of the polarization propagator is probably the
However, the ADC series naturally inherits some of the drawbacks of its MP parent and it has been shown to be not particularly rapidly convergent in the context of vertical excitation energies. \cite{Loos_2018a,Loos_2020a,Veril_2021}
This has led some of the authors to recently propose the ADC(2.5) composite approach, where, in the same spirit as MP2.5, one averages the second-order [ADC(2)] and third-order [ADC(3)] vertical transition energies. \cite{Loos_2020d}
Multi-reference perturbation theory is somewhat easier to generalize to excited states as one selects the states of interest to include in the reference (zeroth-order) space via the so-called complete-active-space self-consistent field (CASSCF) formalism, hence catching effectively static correlation in the zeroth-order wave function.
The missing dynamical correlation can then be recovered via low-order perturbation theory, as performed in the complete-active-space second-order perturbation theory (CASPT2) of Roos and
coworkers, \cite{Andersson_1990,Andersson_1992,Roos_1995a} Hirao's multireference second-order M{\o}llet-Plesset (MRMP2) approach, \cite{Hirao_1992} or the $N$-electron valence state second-order perturbation theory (NEVPT2) developed by Angeli, Malrieu, and coworkers. \cite{Angeli_2001a,Angeli_2001b,Angeli_2002,Angeli_2006}
Multi-reference perturbation theory is somewhat easier to generalize to excited states as one selects the states of interest to include in the reference (zeroth-order) space via the so-called complete-active-space self-consistent field (CASSCF) formalism, hence catching effectively static correlation in the zeroth-order model space.
The missing dynamical correlation can then be recovered in the (first-order) outer space via low-order perturbation theory, as performed in the complete-active-space second-order perturbation theory (CASPT2) of Roos and coworkers, \cite{Andersson_1990,Andersson_1992,Roos_1995a} Hirao's multireference second-order M{\o}llet-Plesset (MRMP2) approach, \cite{Hirao_1992} or the $N$-electron valence state second-order perturbation theory (NEVPT2) developed by Angeli, Malrieu, and coworkers. \cite{Angeli_2001a,Angeli_2001b,Angeli_2002,Angeli_2006}
However, these multi-reference formalisms and their implementation are much more involved and costly than their single-reference counterparts.
Although it has well-document weaknesses, CASPT2 is indisputably the most popular of the three approaches mentioned above.
As such, it has been employed in countless computational studies involving electronic excited states. \cite{Serrano-Andres_1993a,Serrano-Andres_1993b,Serrano-Andres_1993c,Serrano-Andres_1995,Roos_1996,Serrano-Andres_1996a,Serrano-Andres_1996b,Serrano-Andres_1998b,Roos_1999,Merchan_1999,Roos_2002,Serrano-Andres_2002,Serrano-Andres_2005,Tozer_1999,Burcl0_2002,Peach_2008,Faber_2013,Schreiber_2008,Silva-Junior_2008,Sauer_2009,Silva-Junior_2010a,Silva-Junior_2010b,Silva-Junior_2010c}
@ -125,19 +125,22 @@ In the context of excited states, its most severe drawback is certainly the intr
One can then introduce a shift in the denominators to avoid such situations, and correcting afterwards the second-order energy for the use of this shift.
The use of real-valued \cite{Roos_1995b,Roos_1996} or imaginary \cite{Forsberg_1997} level shifts has been successfully tested and is now routine in excited-state calculations. \cite{Schapiro_2013,Zobel_2017,Sarka_2022}
A second drawback was revealed by Andersson \textit{et al.} \cite{Andersson_1993,Andersson_1995} and explained by the unbalanced treatment in the zeroth-order Hamiltonian of the open- and closed-shell electronic configurations.
A second pitfall was revealed by Andersson \textit{et al.} \cite{Andersson_1993,Andersson_1995} and explained by the unbalanced treatment in the zeroth-order Hamiltonian of the open- and closed-shell electronic configurations.
A cure was quickly proposed via the introduction of an additional parameter in the zeroth-order Hamiltonian, the infamous ionization-potential-electron-affinity (IPEA) shift. \cite{Ghigo_2004}
Although the introduction of an IPEA shift can provide a better agreement between experiment and theory, \cite{Pierloot_2006,Pierloot_2008,Suaud_2009,Kepenekian_2009,Daku_2012,Rudavskyi_2014,Vela_2016,Wen_2018} it has been shown by Zobel \textit{et al.} that the application of an IPEA shift is not systematically justified and has been found to be fairly basis set dependent. \cite{Zobel_2017}
Although the introduction of an IPEA shift can provide a better agreement between experiment and theory, \cite{Pierloot_2006,Pierloot_2008,Suaud_2009,Kepenekian_2009,Daku_2012,Rudavskyi_2014,Vela_2016,Wen_2018} it has been shown that its application is not systematically justified and has been found to be fairly basis set dependent. \cite{Zobel_2017}
Recently, based on the highly-accurate vertical excitation energies of the QUEST database, \cite{Loos_2018a,Loos_2019,Loos_2020a,Loos_2020b,Loos_2020c,Veril_2021,Loos_2021c,Loos_2021b} we have reported an exhaustive benchmark of CASPT2 and NEVPT2 for 284 excited states of diverse natures (singlets, triplets, valence, Rydberg, $n\to\pis$, $\pi\to\pis$, and double excitations) computed in 35 small- and medium-sized organic molecules containing from three to six non-hydrogen atoms. \cite{Sarka_2022}
Very recently, based on the highly-accurate vertical excitation energies of the QUEST database, \cite{Loos_2018a,Loos_2019,Loos_2020a,Loos_2020b,Loos_2020c,Veril_2021,Loos_2021c,Loos_2021b} we have reported an exhaustive benchmark of CASPT2 and NEVPT2 for 284 excited states of diverse natures (singlet, triplet, valence, Rydberg, $n\to\pis$, $\pi\to\pis$, and double excitations) computed in 35 small- and medium-sized organic molecules containing from three to six non-hydrogen atoms. \cite{Sarka_2022}
Our main take-home message was that both CASPT2 with IPEA shift and the partially-contracted version of NEVPT2 provide fairly reliable vertical transition energy estimates, with slight overestimations and mean absolute errors of \SI{0.11}{} and \SI{0.13}{\eV}, respectively.
Importantly, the introduction of the IPEA shift in CASPT2 was found to lower the mean absolute errors from \SI{0.27}{} to \SI{0.11}{eV}.
In the electronic structure community, third-order perturbation theory has a fairly bad reputation especially within MP perturbation theory where it is rarely worth its extra cost. \cite{Rettig_2020}
Nonetheless, going against popular believes and one step further in the perturbative expansion, we propose here to assess the performance of the complete-active-space third-order perturbation theory (CASPT3) method developed by Werner \cite{Werner_1996} and implemented in MOLPRO. \cite{Werner_2020}
Very few CASPT3 calculations have been reported in the literature \cite{Angeli_2006,Yanai_2007,Grabarek_2016,Li_2017,Li_2018,Li_2021} with only a single work reporting CASPT3 vertical excitation energies. \cite{Grabarek_2016}
Based on the same 284 vertical excitation energies from the QUEST database, we show that CASPT3 provides a significant improvement compared to CASPT2.
Moreover, as already reported, \cite{Grabarek_2016} we also observe that the accuracy of CASPT3 is much less sensitive to the IPEA shift.
In the electronic structure community, third-order perturbation theory has a fairly bad reputation especially within MP perturbation theory where it is rarely worth its extra computational cost. \cite{Rettig_2020}
Nonetheless, going against popular beliefs and one step further in the perturbative expansion, we propose here to assess the performance of the complete-active-space third-order perturbation theory (CASPT3) method developed by Werner \cite{Werner_1996} and implemented in MOLPRO \cite{Werner_2020} for a significant set of electronic transitions.
Although few CASPT3 calculations have been reported in the literature,
\cite{Angeli_2006,Yanai_2007,Grabarek_2016,Li_2017,Li_2018,Li_2021,Bittererova_2001,Bokarev_2009,Frankcombe_2011,Gu_2008,Kerkines_2005,Lampart_2008,Leininger_2000,Maranzana_2020,Papakondylis_1999,Schild_2013,Sun_2018,Takatani_2009,Takatani_2010,Verma_2018,Woywod_2010,Yan_2004,Zhang_2020,Zhu_2005,Zhu_2007,Zhu_2013,Zou_2009}
the present study provides a comprehensive benchmark of CASPT3 as well as definite answers regarding its overall accuracy in the framework of electronically excited states.
Based on the same 284 highly-accurate vertical excitation energies from the QUEST database, we show that CASPT3 provides a significant improvement compared to CASPT2.
Moreover, as already reported in Ref.~\onlinecite{Grabarek_2016} where CASPT3 excitation energies are reported for retinal chromophore minimal models, we also observe that the accuracy of CASPT3 is much less sensitive to the IPEA shift.
Note that, although a third-order version of NEVPT has been developed \cite{Angeli_2006} and has been used in several applications \cite{Pastore_2006a,Pastore_2006b,Pastore_2007,Angeli_2007,Camacho_2010,Angeli_2011,Angeli_2012} by Angeli and coworkers, as far as we are aware of, only standalone implementation of NEVPT3 exists.
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@ -153,9 +156,9 @@ Note that, although a third-order version of NEVPT has been developed \cite{Ange
\end{figure}
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For each compounds represented in Fig.~\ref{fig:mol}, we have computed the CASPT2 and CASPT3 vertical excitation energies with Dunning's aug-cc-pVTZ
For each compound represented in Fig.~\ref{fig:mol}, we have computed the CASPT2 and CASPT3 vertical excitation energies with Dunning's aug-cc-pVTZ
basis set. \cite{Kendall_1992}
Geometries have been extracted from the QUEST database \cite{Veril_2021} and can be downloaded at \url{https://lcpq.github.io/QUESTDB_website}.
Geometries and reference theoretical best estimates (TBEs) of the vertical excitation energies have been extracted from the QUEST database \cite{Veril_2021} and can be downloaded at \url{https://lcpq.github.io/QUESTDB_website}.
All the CASPT2 and CASPT3 calculations have been carried out with MOLPRO within the RS2 and RS3 contraction schemes as described in Refs.~\onlinecite{Werner_1996} and \onlinecite{Werner_2020}.
Both methods have been tested with and without IPEA (labeled as NOIPEA).
@ -167,7 +170,7 @@ In several occasions, we have included additional excited states to avoid conver
For each system and transition, we report in the {\SupInf} the exhaustive description of the active spaces for each symmetry sector.
Additionally, for the challenging transitions, we have steadily increased the size of the active space to carefully assess the convergence of the vertical excitation energies of interest.
Finally, to alleviate the intruder state problem, a level shift of \SI{0.3}{\hartree} has been systematically applied. \cite{Roos_1995b,Roos_1996}
This value has been slightly increased in particularly difficult cases, and is specifically reported.
This value has been slightly increased in particularly difficult cases, and is specifically reported in such cases.
The usual statistical indicators are used in the following, namely, the mean signed error (MSE), the mean absolute error (MAE), the root-mean-square error (RMSE), the standard
deviation of the errors (SDE), as well as largest positive and negative deviations [Max($+$) and Max($-$), respectively].
@ -177,7 +180,7 @@ deviation of the errors (SDE), as well as largest positive and negative deviatio
\label{sec:res}
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A detailed discussion of each individual molecule can be found in Ref.~\onlinecite{Sarka_2022} where we report relevant values from the literature.
A detailed discussion of each individual molecule can be found in Ref.~\onlinecite{Sarka_2022} where we also report relevant values from the literature.
Here, we focus on global trends.
The exhaustive list of CASPT2 and CASPT3 transitions can be found in Table \ref{tab:BigTab} and are represented in Fig.~\ref{fig:}.