24 KiB
24 KiB
RSDFT-CIPSI
- H2O
- C2
Geometries are given in Angstrom. Basis sets and pseudopotentials are given in GAMESS(US) format. $$ \mu_i \approx \frac{1}{2} \frac{1.5^{i}}{1.5^3} $$
H2O
Reference atomization energy : 0.371900 au
XYZ file
Same Geometry as in doi:10.1063/1.4947093
3 Water from doi:10.1063/1.4947093 O 0. 0. 0. H -0.756950272703377558 0. -0.585882234512562827 H 0.756950272703377558 0. -0.585882234512562827
Nuclear repulsion energy : 6.983610526929691
Pseudopotential
H GEN 0 0 3 1.00000000 1 4.47692410 4.47692410 3 2.97636451 -4.32112340 2 3.01841596 O GEN 2 1 3 6.00000000 1 9.29793903 55.78763416 3 8.86492204 -38.81978498 2 8.62925665 1 38.41914135 2 8.71924452
cc-pVDZ-BFD
HYDROGEN S 9 1 0.013000 0.000706 2 0.029900 -0.002119 3 0.068770 0.057693 4 0.158170 0.230695 5 0.363792 0.277612 6 0.836721 0.169833 7 1.924458 0.097443 8 4.426254 0.029966 9 10.180385 -0.000452 S 1 1 0.170483 1.000000 P 9 1 0.003000 0.001242 2 0.007800 -0.000913 3 0.020281 -0.000054 4 0.052730 -0.000238 5 0.137097 -0.011530 6 0.356451 -0.018235 7 0.926774 -0.013929 8 2.409612 -0.009395 9 6.264991 -0.000347 OXYGEN S 9 1 0.125346 0.055741 2 0.268022 0.304848 3 0.573098 0.453752 4 1.225429 0.295926 5 2.620277 0.019567 6 5.602818 -0.128627 7 11.980245 0.012024 8 25.616801 0.000407 9 54.775216 -0.000076 S 1 1 0.258551 1.000000 P 9 1 0.083598 0.044958 2 0.167017 0.150175 3 0.333673 0.255999 4 0.666627 0.281879 5 1.331816 0.242835 6 2.660761 0.161134 7 5.315785 0.082308 8 10.620108 0.039899 9 21.217318 0.004679 P 1 1 0.267865 1.000000 D 1 1 1.232753 1.000000
24 AOs, 23 MOs
HF energy:
H2O | -16.94804007785208 |
H | -0.4990452313322324 |
O | -15.70594174131179 |
CCSD(T) dissociation energy: 0.333219 au
CIPSI with natural orbitals
#+NAME:h2o-dz-bfd
H2O | H | O | |||||
---|---|---|---|---|---|---|---|
$\mu$ | Ndet | E(CIPSI) | Ndet | E(CIPSI) | Ndet | E(CIPSI) | E_atomization |
1.e-6 | 11 | -17.2464827355670 | 1 | -0.497462910963732 | 32 | -15.8926592152696 | 0.35889770 |
0.20 | 23 | -17.2454472136151 | 1 | -0.497675271883671 | 18 | -15.8906553675359 | 0.35944130 |
0.30 | 53 | -17.2531752249923 | 1 | -0.500020054995876 | 22 | -15.8991860505193 | 0.35394906 |
0.50 | 1442 | -17.2627954176401 | 1 | -0.502301769176686 | 95 | -15.9113115088349 | 0.34688037 |
0.75 | 3213 | -17.2608600031439 | 1 | -0.501902392897537 | 431 | -15.9125649495245 | 0.34449027 |
1.00 | 6743 | -17.2526327790576 | 1 | -0.500915129067989 | 571 | -15.9054097072708 | 0.34539281 |
1.75 | 54540 | -17.2227612803246 | 1 | -0.499556360741909 | 1064 | -15.8778827081260 | 0.34576585 |
2.50 | 51691 | -17.2017620477491 | 1 | -0.499220775536428 | 1879 | -15.8599672611832 | 0.34335324 |
3.80 | 103059 | -17.1841520428494 | 1 | -0.499087178764149 | 1846 | -15.8450343476922 | 0.34094334 |
5.70 | 102599 | -17.1743644569390 | 1 | -0.499054690526038 | 1944 | -15.8372541996167 | 0.33900088 |
8.50 | 101803 | -17.1692969615481 | 1 | -0.499047296040090 | 1943 | -15.8333886253435 | 0.33781374 |
$\intfy$ | 200521 | -17.1644196532044 | 1 | -0.49904523 | 15699 | -15.8300247094224 | 0.33630448 |
ExFCI | NA | -17.164669 | 1 | -0.49904523 | NA | -15.83002472 | 0.33655382 |
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QMC
#+NAME:h2o-dz-bfd-qmc
H2O | H | O | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
$\mu$ | Ndet | E(DMC) | Error | Ndet | E(DMC) | Error | Ndet | E(DMC) | Error | E_atomization | |
1.e-6 | 11 | 1 | -0.5000010174 | 0.0000172350 | -1.0000020 | 2.4373971e-5 | |||||
0.20 | 23 | 1 | -0.5000031727 | 0.0000098305 | -1.0000063 | 1.3902426e-5 | |||||
0.30 | 53 | 1 | -0.5000014039 | 0.0000201664 | -1.0000028 | 2.8519596e-5 | |||||
0.50 | 1442 | 1 | -0.4999990746 | 0.0000135287 | -0.99999815 | 1.9132471e-5 | |||||
0.75 | 3213 | 1 | -0.4999704651 | 0.0000123770 | -0.99994093 | 1.7503721e-5 | |||||
1.00 | 6743 | 1 | -0.4999828909 | 0.0000123869 | -0.99996578 | 1.7517722e-5 | |||||
1.75 | 54540 | 1 | -0.4999832501 | 0.0000118522 | -0.99996650 | 1.6761542e-5 | |||||
2.50 | 51691 | 1 | -0.5000182128 | 0.0000122194 | -1.0000364 | 1.7280841e-5 | |||||
3.80 | 103059 | 1 | -0.4999868144 | 0.0000178879 | -0.99997363 | 2.5297311e-5 | |||||
5.70 | 102599 | 1 | -0.5000137286 | 0.0000197492 | -1.0000275 | 2.7929586e-5 | |||||
8.50 | 101803 | 1 | -0.4999852648 | 0.0000097121 | -0.99997053 | 1.3734984e-5 | |||||
inf | 200521 | 1 | -0.5000103856 | 0.0000211133 | -1.0000208 | 2.9858715e-5 |
cc-pVTZ-BFD
HYDROGEN S 9 1 0.013000 0.000706 2 0.029900 -0.002119 3 0.068770 0.057693 4 0.158170 0.230695 5 0.363792 0.277612 6 0.836721 0.169833 7 1.924458 0.097443 8 4.426254 0.029966 9 10.180385 -0.000452 S 1 1 0.170654 1.000000 P 9 1 0.003000 0.001242 2 0.007800 -0.000913 3 0.020281 -0.000054 4 0.052730 -0.000238 5 0.137097 -0.011530 6 0.356451 -0.018235 7 0.926774 -0.013929 8 2.409612 -0.009395 9 6.264991 -0.000347 P 1 1 0.495357 1.000000 D 1 1 0.955745 1.000000 OXYGEN S 9 1 0.125346 0.055741 2 0.268022 0.304848 3 0.573098 0.453752 4 1.225429 0.295926 5 2.620277 0.019567 6 5.602818 -0.128627 7 11.980245 0.012024 8 25.616801 0.000407 9 54.775216 -0.000076 S 1 1 1.686633 1.000000 S 1 1 0.237997 1.000000 P 9 1 0.083598 0.044958 2 0.167017 0.150175 3 0.333673 0.255999 4 0.666627 0.281879 5 1.331816 0.242835 6 2.660761 0.161134 7 5.315785 0.082308 8 10.620108 0.039899 9 21.217318 0.004679 P 1 1 0.184696 1.000000 P 1 1 0.600621 1.000000 D 1 1 0.669340 1.000000 D 1 1 2.404278 1.000000 F 1 1 1.423104 1.000000
62 AOs, 55 MOs
HF energy:
H2O | -16.95323238971265 |
H | -0.4990429174703885 |
O | -15.70800126366209 |
CCSD(T) dissociation energy: 0.359559 au
CIPSI with natural orbitals
H2O | H | O | |||||
---|---|---|---|---|---|---|---|
$\mu$ | Ndet | E(CIPSI) | Ndet | E(CIPSI) | Ndet | E(CIPSI) | E_atomization |
1.e-6 | 23 | -17.2523870798208 | 1 | -0.497455949623173 | 56 | -15.8943418199011 | 0.36313336 |
0.20 | 23 | -17.2517850749956 | 1 | -0.497667829593971 | 44 | -15.8925846521328 | 0.36386476 |
0.30 | 219 | -17.2602989385967 | 1 | -0.500012863167701 | 44 | -15.9011337704962 | 0.35913944 |
0.50 | 1699 | -17.2712812851578 | 1 | -0.502296128041502 | 387 | -15.9149780380730 | 0.35171099 |
0.75 | 13362 | -17.2742507881653 | 1 | -0.501898409513286 | 1133 | -15.9199259292212 | 0.35052804 |
1.00 | 25673 | -17.2705814448750 | 1 | -0.500911996264451 | 2291 | -15.9169272791252 | 0.35183017 |
1.75 | 207475 | -17.2550176120029 | 1 | -0.499553910797633 | 9594 | -15.9020240076499 | 0.35388578 |
2.50 | 858123 | -17.2461435031256 | 1 | -0.499218425280479 | 21911 | -15.8938546433323 | 0.35385201 |
3.80 | 1621513 | -17.2393621693893 | 1 | -0.499084857864629 | 18329 | -15.8877260665965 | 0.35346639 |
5.70 | 1629655 | -17.2358436456985 | 1 | -0.499052375301986 | 21941 | -15.8850092841849 | 0.35272961 |
8.50 | 1643301 | -17.2339427191574 | 1 | -0.499044981913016 | 42217 | -15.8838759830564 | 0.35197677 |
$\intfy$ | 1631982 | -17.2316182510754 | 1 | -0.499042917477163 | 282793 | -15.8825637842011 | 0.35096863 |
ExFCI | -17.23217115 | -0.499042917477163 | -15.88257866 | 0.35150666 |
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cc-pVQZ-BFD
HYDROGEN S 9 1 0.013000 0.000706 2 0.029900 -0.002119 3 0.068770 0.057693 4 0.158170 0.230695 5 0.363792 0.277612 6 0.836721 0.169833 7 1.924458 0.097443 8 4.426254 0.029966 9 10.180385 -0.000452 S 1 1 0.120599 1.000000 S 1 1 0.404783 1.000000 S 1 1 0.715129 1.000000 P 9 1 0.003000 0.001242 2 0.007800 -0.000913 3 0.020281 -0.000054 4 0.052730 -0.000238 5 0.137097 -0.011530 6 0.356451 -0.018235 7 0.926774 -0.013929 8 2.409612 -0.009395 9 6.264991 -0.000347 P 1 1 0.774536 1.000000 P 1 1 0.263038 1.000000 D 1 1 2.315883 1.000000 D 1 1 0.636656 1.000000 F 1 1 1.130819 1.000000 OXYGEN S 9 1 0.125346 0.055741 2 0.268022 0.304848 3 0.573098 0.453752 4 1.225429 0.295926 5 2.620277 0.019567 6 5.602818 -0.128627 7 11.980245 0.012024 8 25.616801 0.000407 9 54.775216 -0.000076 S 1 1 0.224380 1.000000 S 1 1 0.843157 1.000000 S 1 1 1.351771 1.000000 P 9 1 0.083598 0.044958 2 0.167017 0.150175 3 0.333673 0.255999 4 0.666627 0.281879 5 1.331816 0.242835 6 2.660761 0.161134 7 5.315785 0.082308 8 10.620108 0.039899 9 21.217318 0.004679 P 1 1 0.148562 1.000000 P 1 1 0.452364 1.000000 P 1 1 1.106737 1.000000 D 1 1 0.455711 1.000000 D 1 1 1.344331 1.000000 D 1 1 4.008867 1.000000 F 1 1 0.876289 1.000000 F 1 1 2.763115 1.000000 G 1 1 1.759081 1.000000
139 AOs, 114 MOs
HF energy:
H2O | -16.95323238971265 |
H | -0.4999159485752356 |
O | -15.70838239857190 |
CCSD(T) dissociation energy: ??? au
CIPSI with natural orbitals
#+NAME:h2o-qz-bfd
H2O | H | O | ||||||||
---|---|---|---|---|---|---|---|---|---|---|
$\mu$ | Ndet | E(CIPSI) | Ndet | E(CIPSI) | Ndet | E(CIPSI) | E_atomization | |||
1.e-6 | 1 | -0.498770397586525 | 41 | -15.8945440099478 | -16.892085 | |||||
0.20 | 1 | -0.498943556678728 | 39 | -15.8927491298105 | -16.890636 | |||||
0.30 | 1 | -0.501238867081562 | 88 | -15.9015447645282 | -16.904022 | |||||
0.50 | 1 | -0.503289490954576 | 369 | -15.9156299499914 | -16.922209 | |||||
0.75 | 1 | -0.502729685060127 | 2152 | -15.9216014051348 | -16.927061 | |||||
1.00 | 1 | -0.501722057158799 | 4324 | -15.9193017992612 | -16.922746 | |||||
1.75 | 1 | -0.500400995599045 | 14431 | -15.9068519442068 | -16.907654 | |||||
2.50 | 1 | -0.500081369220756 | 30186 | -15.9011704544825 | -16.901333 | |||||
3.80 | 1 | -0.499955311987831 | 94180 | -15.8985952759131 | -16.898506 | |||||
5.70 | 6846023 | -17.2565768115301 | 1 | -0.499924811823201 | 101131 | -15.8978811997698 | 0.35884599 | |||
8.50 | 6501453 | -17.2563271562921 | 1 | -0.499917882290281 | 94108 | -15.8976152329438 | 0.35887616 | |||
$\intfy$ | 6555322 | -17.2555127230293 | 1 | -0.499915948575730 | 1614219 | -15.8976190012628 | 0.35806182 | |||
ExFCI | -17.25606450 | -0.499915948575730 | -15.89763971 | 0.35859289 |
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All-electron
C2
Data taken from doi:10.1021/ct300504f Reference atomization energy : 146.9(5) kcal/mol = 0.2341(8) au
XYZ file
Same Geometry as in doi:10.1021/ct300504f
2 C2 C 0. 0. -0.62125 C 0. 0. 0.62125
Nuclear repulsion energy : 6.814354426334003
Pseudopotential
C GEN 2 1 3 4.00000000 1 8.35973821 33.43895285 3 4.48361888 -19.17537323 2 3.93831258 1 22.55164191 2 5.02991637
cc-pVDZ-BFD
CARBON S 9 1 0.051344 0.013991 2 0.102619 0.169852 3 0.205100 0.397529 4 0.409924 0.380369 5 0.819297 0.180113 6 1.637494 -0.033512 7 3.272791 -0.121499 8 6.541187 0.015176 9 13.073594 -0.000705 S 1 1 0.127852 1.000000 P 9 1 0.029281 0.001787 2 0.058547 0.050426 3 0.117063 0.191634 4 0.234064 0.302667 5 0.468003 0.289868 6 0.935757 0.210979 7 1.871016 0.112024 8 3.741035 0.054425 9 7.480076 0.021931 P 1 1 0.149161 1.000000 D 1 1 0.561160 1.000000
28 AOs, 26 MOs
HF energy:
C2 | -10.67893455005543 |
C | -5.328989707682060 |
i-FCIQMC dissociation energy: 129.95(8) kcal/mol = 0.2071(1) au
CIPSI with natural orbitals
#+NAME:c2-dz-bfd
C2 | C | ||||
---|---|---|---|---|---|
$\mu$ | Ndet | E(CIPSI) | Ndet | E(CIPSI) | E_atomization |
1.e-6 | 22 | -5.41505706988073 | -10.830114 | ||
0.20 | 9 | -5.41545184840256 | -10.830904 | ||
0.30 | 21 | -5.42042892115798 | -10.840858 | ||
0.50 | 135 | -5.42445651484712 | -10.848913 | ||
0.75 | 163 | -5.42281416310061 | -10.845628 | ||
1.00 | 330 | -5.42008673295876 | -10.840173 | ||
1.75 | 408078 | -11.0314740806244 | 509 | -5.41456475332999 | 0.20234457 |
2.50 | 822205 | -11.0291998069478 | 513 | -5.41233203015442 | 0.20453575 |
3.80 | 703001 | -11.0267092471890 | 511 | -5.41095120348554 | 0.20480684 |
5.70 | 715415 | -11.0251197032813 | 498 | -5.41028104327860 | 0.20455762 |
8.50 | 1421782 | -11.0243736638120 | 498 | -5.40994218754541 | 0.20448929 |
$\intfy$ | 722672 | -11.0229208360228 | 498 | -5.40958049910186 | 0.20375984 |
ExFCI | NA | -11.02347855 | -5.40960365 | 0.20427125 |
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cc-pVTZ-BFD
CARBON S 9 1 0.051344 0.013991 2 0.102619 0.169852 3 0.205100 0.397529 4 0.409924 0.380369 5 0.819297 0.180113 6 1.637494 -0.033512 7 3.272791 -0.121499 8 6.541187 0.015176 9 13.073594 -0.000705 S 1 1 0.921552 1.000000 S 1 1 0.132800 1.000000 P 9 1 0.029281 0.001787 2 0.058547 0.050426 3 0.117063 0.191634 4 0.234064 0.302667 5 0.468003 0.289868 6 0.935757 0.210979 7 1.871016 0.112024 8 3.741035 0.054425 9 7.480076 0.021931 P 1 1 0.126772 1.000000 P 1 1 0.376742 1.000000 D 1 1 0.329486 1.000000 D 1 1 1.141611 1.000000 F 1 1 0.773485 1.000000
_ AOs, _ MOs
HF energy:
C2 | |
C |
i-FCIQMC dissociation energy: 139.69(8) kcal/mol = 0.2226(1) au
CIPSI with natural orbitals
C2 | C | ||||
---|---|---|---|---|---|
$\mu$ | Ndet | E(CIPSI) | Ndet | E(CIPSI) | E_atomization |
1.e-6 | 0. | ||||
0.20 | 0. | ||||
0.30 | 0. | ||||
0.50 | 0. | ||||
0.75 | 0. | ||||
1.00 | 0. | ||||
1.75 | 0. | ||||
2.50 | 0. | ||||
3.80 | 0. | ||||
5.70 | 0. | ||||
8.50 | 0. | ||||
$\intfy$ | 722672 | 0. | |||
ExFCI | NA | -11.02343265 | -5.40960365 | 0.20422535 |
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set xrange [0.01:100]
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cc-pVQZ-BFD
CARBON S 9 1 0.051344 0.013991 2 0.102619 0.169852 3 0.205100 0.397529 4 0.409924 0.380369 5 0.819297 0.180113 6 1.637494 -0.033512 7 3.272791 -0.121499 8 6.541187 0.015176 9 13.073594 -0.000705 S 1 1 0.109576 1.000000 S 1 1 0.846879 1.000000 S 1 1 0.269659 1.000000 P 9 1 0.029281 0.001787 2 0.058547 0.050426 3 0.117063 0.191634 4 0.234064 0.302667 5 0.468003 0.289868 6 0.935757 0.210979 7 1.871016 0.112024 8 3.741035 0.054425 9 7.480076 0.021931 P 1 1 0.105389 1.000000 P 1 1 0.313254 1.000000 P 1 1 0.804681 1.000000 D 1 1 0.240171 1.000000 D 1 1 0.684884 1.000000 D 1 1 2.013760 1.000000 F 1 1 0.457302 1.000000 F 1 1 1.324930 1.000000 G 1 1 1.034180 1.000000
__ AOs, _ MOs HF energy:
HF energy:
C2 | |
C |
CCSD(T) dissociation energy: ??? au
CIPSI with natural orbitals
#+NAME:c2-qz-bfd
C2 | C | ||||
---|---|---|---|---|---|
$\mu$ | Ndet | E(CIPSI) | Ndet | E(CIPSI) | E_atomization |
1.e-6 | 0. | ||||
0.20 | 0. | ||||
0.30 | 0. | ||||
0.50 | 0. | ||||
0.75 | 0. | ||||
1.00 | 0. | ||||
1.75 | 0. | ||||
2.50 | 0. | ||||
3.80 | 0. | ||||
5.70 | 0. | ||||
8.50 | 0. | ||||
$\intfy$ | 722672 | 0. | |||
ExFCI | NA | -11.02343265 | -5.40960365 | 0.20422535 |
reset
set log x
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set xrange [0.01:100]
set xtics 0.1
plot data u 1:8 w lp notitle