solvent effects electron correlation effects nonaddiabatic effects relativistic
Отчитане на ефекти в квантовохимичните изчисления solvent effects ’electron correlation effects’ ’non-addiabatic effects’ ’relativistic effects’ http: //home. cc. umanitoba. ca/~schrecke/Pictures/research_page_pictures/ACR 2010 TOC_small. jpg Грешките в пресметнатите свойства са толкова по-големи, колкото по-тежък е атомът!
Two-component relativistic methods: Двукомпонентните Хамилтониани са получени чрез трансформиране на четирикомпонентния Хамилтониан на Dirac– Coulomb в двукомпонентна форма чрез разделяне на големите и малките компоненти. Начинът на разделяне може да е различен. Най-популярните схеми са: • the regular approximation zero-order regular approximation (ZORA) first-order regular approximation (FORA) infinite-order regular approximation with modified metric (IORAmm). Spin-free ZORA Hamiltonian (without spin-orbit coupling term) is actually a one-component Hamiltonian. • the Douglas–Kroll–Hess approximation
Relativistic Elimination of the Small Component (RESC) #UB 3 LYP/ 6 -31 G* Integral=RESC Requests a RESC scalar relativistic calculation. Мeтодът не е вариационен!
Три подхода: 1. Използване на базиси, които автоматично включват ECPs за вътрешните електрони на тежките атоми: SHC: D 95 V on first row, Goddard/Smedley ECP on second row. Also known as SEC. CEP-4 G: Stevens/Basch/Krauss ECP minimal basis. CEP-31 G: CEP-31 G Stevens/Basch/Krauss ECP split valance. CEP-121 G: Stevens/Basch/Krauss ECP triple-split basis. Note that there is only one CEP basis set defined beyond the second row, and all three keywords are equivalent for these atoms. Lan. L 2 MB: STO-3 G on first row, Los Alamos ECP plus MBS on Na-La, Hf-Bi. Lan. L 2 DZ: Lan. L 2 DZ D 95 V on first row, Los Alamos ECP plus DZ on Na-La, Hf-Bi. SDD: SDD D 95 up to Ar and Stuttgart/Dresden ECPs on the remainder of the periodic. G 09 def 2 -XZVP TURBOMOLE
2. Използване на базиси, които са напаснати по релативистични пресматания за атоми (Stuttgart RLC ECP ; aug-cc-p. V 5 Z-DK) #RHF/gen Pseudo=Read Opt CHON 0 6 -31 G* **** Cs 0 S 3 1. 00 0. 3974310 …. 0. 0095740 **** CS 0 CS-ECP 3 54 f-ul potential 1 2 1. 00000 s-ul potential 1 2 1. 160000000 p-ul potential 1 2 0. 244700000 d-ul potential 1 2 0. 242700000 0. 2396470 1. 0000000 0. 00000 303. 50000 2. 930000000 -1. 138000000 G 09
Structure ED, a. u. EQ, a. u. ES, a. u. EDQ, kcal/mol EDS, kcal/mol G 09 ORCA Structure 11 ED, a. u. EQ, a. u. ES, a. u. EDQ, kcal/mol EDS, kcal/mol <S 2>D <S 2>Q <S 2>S (Mn) D (Mn) Q (Mn) S CPU time (D) CPU time (Q) CPU time (S) 6 -31 G* -1841. 293783 -1841. 316774 -1841. 389921 14. 427 60. 328 2. 540 3. 774 8. 755 1. 002 3. 049 4. 872 03: 02: 36 00: 10: 54 00: 03: 41 6 -31 G* -1841. 309744 -1841. 341330 -1841. 405766 19. 821 60. 255 6 -31 G*/DKH -1847. 672422 -1847. 704075 -1847. 768574 19. 863 60. 336 -1848. 123659 -1848. 155313 -1848. 219810 19. 863 60. 336 2. 519 4. 582 8. 755 0. 999 2. 993 4. 870 09: 47: 54 05: 58: 02 00: 59 2. 563 4. 582 8. 756 1. 019 2. 994 4. 876 15: 41: 53 07: 33: 01 01: 14: 27 2. 563 4. 582 8. 756 1. 019 2. 994 4. 876 15: 42: 07 07: 45: 32 01: 10: 16 <S 2>D <S 2>Q <S 2>S (Mn) D (Mn) Q (Mn) S CPU time (D) CPU time (Q) CPU time (S) 6 -31 G*/DKH -1847. 609611 -1847. 670579 -1847. 743914 38. 258 84. 276 0. 757 3. 774 8. 755 1. 020 3. 050 4. 877 00: 49: 59 00: 25: 01 00: 03: 16 6 -31 G*/ ZORA -1853. 215501 -1853. 253778 -1853. 327106 24. 019 70. 033 1. 971 3. 775 8. 755 1. 043 3. 050 4. 878 04: 21: 12 00: 18: 10 00: 03: 38 TZVPP -1838. 714866 -1838. 737185 -1838. 764658 14. 005 31. 245 2. 245 4. 172 8. 770 1. 003 3. 068 5. 059 03: 02: 28 03: 10: 01 02: 21: 09 TZVPP/DKH -----1849. 657535 -1849. 726011 ------3. 781 8. 757 ----3. 051 4. 855 ----27: 25: 49 00: 50: 49 6 -31 G*/ RESC TZVPP/ ZORA -1854. 217074 -1854. 273449 -1854. 339286 35. 376 76. 689 0. 761 3. 780 8. 757 1. 040 3. 048 4. 855 37: 18: 49 02: 23: 55 01: 00: 24
G 09 ORCA Basis set ED, a. u. EQ, a. u. ES, a. u. EDQ, kcal/mol EDS, kcal/mol <S 2>D <S 2>Q <S 2>S (Mn) D (Mn) Q (Mn) S CPU time (D) CPU time (Q) CPU time (S) 6 -31 G* -1841. 309744 -1841. 341330 -1841. 405766 19. 821 60. 255 2. 519 4. 582 8. 755 0. 999 2. 993 4. 870 09: 47: 54 05: 58: 02 00: 50: 59 LANL 2 DZ -794. 252963 -794. 280636 -794. 340940 17. 365 55. 206 2. 485 4. 555 8. 755 1. 008 2. 978 4. 792 11: 17: 30 03: 25: 33 00: 31: 22 CEP-31 G -232. 524547 -232. 553261 -232. 614901 18. 018 56. 698 2. 476 4. 559 8. 758 0. 991 2. 985 4. 844 07: 01: 15 03: 10: 45 00: 33: 39 def 2 -TZVP -1841. 724839 -1841. 754411 -1841. 814338 18. 557 56. 161 2. 473 4. 545 8. 756 1. 017 3. 005 4. 851 285: 35: 00 71: 35: 58 14: 01: 37 cc-p. VTZ -1841. 733363 -1841. 762482 -1841. 821311 18. 272 55. 188 2. 473 4. 543 8. 757 0. 989 2. 984 4. 825 587: 49: 44 221: 45: 40 24: 58: 36 aug-cc-p. VTZ -1841. 772120 -1841. 831086 4. 544 8. 756 3. 011 4. 879 2621: 19: 15 256: 55: 18 6 -31 G*/ CEP-31 G 6 -31 G*/ LANL 2 DZ 6 -31 G*/ MDF 10 -1092. 841059 -1092. 787243 -1092. 708485 -33. 770 -83. 191 0. 787 3. 780 8. 818 0. 571 1. 402 2. 550 01: 22: 36 01: 27: 13 01: 18: 14 -794. 318162 -794. 345627 -794. 404942 17. 235 54. 455 2. 471 4. 540 8. 756 1. 012 2. 980 4. 775 21: 18: 07 07: 35: 32 01: 08: 01 -793. 521613 -793. 551031 -793. 614158 18. 458 58. 073 2. 563 4. 584 8. 756 1. 016 2. 991 4. 882 21: 58: 42 07: 29: 41 01: 11: 23
Galilean Transformation Lorentz Transformation
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