New pecJ-n (n = 1, 2) Basis Sets for High-Quality Calculations of Indirect Nuclear Spin–Spin Coupling Constants Involving 31P and 29Si: The Advanced PEC Method
Abstract
:1. Introduction
2. Results and Discussion
2.1. On the Creation of New pecJ-n (n = 1, 2) Basis Sets for Phosphorus and Silicon
2.2. The Performance of New pecJ-n (n = 1, 2) Basis Sets
3. Computational Details
4. Concluding Remarks
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Original dyall.aae4z | dyall.aae4z+ | Additional ζi |
---|---|---|
H: (12s, 4p, 3d, 2f) | +3s | ζ1 = 1.42009326 × 106 ζ2 = 2.05353505 × 105 ζ3 = 2.96952766 × 104 |
C: (19s, 11p, 6d, 4f, 2g) | +2s | ζ1 = 6.64165270 × 107 ζ2 = 9.15768223 × 106 |
Si, P: (25s, 15p, 10d, 7f, 4g) | +1s | Si: ζ1 = 3.37124315 × 108 P: ζ1 = 3.68247433 × 108 |
Basis Set | Simple Contraction Scheme | Extended Contraction Scheme | Nc/Nuc |
---|---|---|---|
pecJ-1 | (14s, 8p, 3d|8s, 5p, 3d) | 8s: (8, 8, 1, 1, 1, 1, 1, 1) 5p: (5, 5, 1, 1, 1) 3d: (1, 1, 1) | 38/53 |
pecJ-2 | (17s, 9p, 4d, 1f|10s, 6p, 4d, 1f) | 10s: (9, 9, 1, 1, 1, 1, 1, 1, 1, 1) 6p: (5, 5, 1, 1, 1, 1) 4d: (1, 1, 1, 1) 1f: (1) | 55/71 |
# | Molecule | SSCC 1 | dyall.aae4z+ 2 | pecJ-1 | pecJ-2 | pcJ-1 | pcJ-2 | aug-cc-pVTZ-J |
---|---|---|---|---|---|---|---|---|
1 | Phosphabenzene | 1J(P,C2) | −46.27 | −37.68 | −43.13 | −29.57 | −42.41 | −42.82 |
2J(P,C3) | −19.88 | −19.72 | −19.87 | −20.23 | −20.16 | −19.99 | ||
3J(P,C4) | 29.52 | 28.78 | 29.27 | 28.46 | 29.44 | 28.40 | ||
2J(P,H2) | 32.96 | 30.81 | 32.34 | 30.81 | 32.05 | 33.28 | ||
3J(P,H3) | 9.49 | 9.61 | 9.27 | 9.66 | 9.40 | 9.49 | ||
4J(P,H4) | −7.01 | −7.13 | −6.74 | −6.89 | −7.08 | −6.84 | ||
2 | P≡CH Phosphaethyne | 1J(P,C) | 78.11 | 74.25 | 76.46 | 90.63 | 73.94 | 76.83 |
2J(P,H) | 53.72 | 50.97 | 53.03 | 51.87 | 52.34 | 52.59 | ||
3 | H2N–PH2 Phosphanamine | 1J(P,N) | −3.73 | 0.93 | −2.65 | 1.71 | −2.50 | −3.85 |
1J(P,H) | 191.34 | 188.90 | 190.64 | 189.73 | 191.82 | 191.61 | ||
2J(P,H) | 11.81 | 10.91 | 11.49 | 11.98 | 11.35 | 11.61 | ||
4 | O=PH3 Phosphine oxide | 1J(P,H) | 445.05 | 441.47 | 441.86 | 439.92 | 446.41 | 445.73 |
5 | PF3 Phosphorus trifluoride | 1J(P, F) | −1409.57 | −1430.81 | −1381.37 | −1337.65 | −1382.72 | −1402.76 |
6 | Methylphosphane | 1J(P,C) | 0.00 | 5.84 | 2.00 | 10.03 | 3.43 | 0.73 |
1J(P,Hα) | 195.19 | 194.72 | 194.30 | 190.91 | 195.49 | 195.81 | ||
2J(P,Hβ) | 7.56 | 6.24 | 6.94 | 6.65 | 6.94 | 7.26 | ||
2J(P,Hβ’) | −8.81 | −9.08 | −9.07 | −9.05 | −9.16 | −9.24 | ||
7 | H2P–F Fluorophosphane | 1J(P,F) | −798.09 | −821.89 | −790.47 | −736.60 | −782.17 | −810.23 |
1J(P,H) | 191.59 | 190.72 | 192.66 | 193.93 | 192.24 | 191.96 | ||
8 | PH3 Phosphane | 1J(P,H) | 190.63 | 190.52 | 190.46 | 184.99 | 190.56 | 191.18 |
9 | Methylenephosphane | 1J(P,C) | −25.56 | −15.30 | −22.50 | −7.66 | −21.78 | −21.93 |
1J(P,Hα) | 131.63 | 126.48 | 132.19 | 126.73 | 129.69 | 132.85 | ||
2J(P,Hβ) | −33.11 | −31.93 | −32.87 | −31.12 | −33.73 | −33.84 | ||
2J(P,Hβ’) | 24.18 | 21.36 | 23.02 | 23.38 | 22.95 | 24.04 | ||
10 | F2P–H Difluorophosphane | 1J(P,H) | 201.52 | 198.47 | 202.60 | 209.59 | 202.51 | 201.56 |
1J(P,F) | −1152.93 | −1168.95 | −1133.17 | −1074.49 | −1124.99 | −1152.84 | ||
11 | H2C=SiH2 Methylenesilane | 1J(Si,C) | −130.07 | −132.52 | −131.53 | −137.73 | −132.39 | −132.47 |
1J(Si,H) | −241.84 | −241.10 | −240.39 | −244.05 | −244.16 | −241.78 | ||
2J(Si,H) | 4.85 | 7.40 | 5.58 | 8.28 | 5.91 | 5.21 | ||
12 | CH≡SiH Methylidynesilane | 1J(Si,C) | −378.85 | −375.00 | −377.57 | −381.61 | −380.36 | −382.16 |
1J(Si,H) | −445.90 | −445.84 | −443.48 | −452.96 | −450.82 | −446.72 | ||
2J(Si,H) | −112.00 | −104.22 | −109.70 | −98.79 | −108.23 | −111.40 | ||
13 | Silanamine | 1J(Si,N) | −15.26 | −16.17 | −15.61 | −16.56 | −15.96 | −15.67 |
1J(Si,Hα) | −199.09 | −197.59 | −197.50 | −199.06 | −200.47 | −199.21 | ||
1J(Si,Hα’) | −188.85 | −186.41 | −187.08 | −186.78 | −189.67 | −188.83 | ||
2J(Si,Hβ) | −1.11 | −0.80 | −1.04 | −1.05 | −1.10 | −1.04 | ||
14 | Silanimine | 1J(Si,N) | −4.53 | −5.37 | −4.73 | −6.39 | −4.81 | −5.02 |
1J(Si,Hα) | −214.71 | −208.67 | −211.00 | −209.13 | −213.74 | −214.03 | ||
1J(Si,Hα’) | −273.58 | −271.32 | −271.49 | −275.74 | −276.00 | −273.58 | ||
2J(Si,Hβ) | 0.88 | 2.38 | 1.36 | 2.15 | 1.26 | 1.15 | ||
15 | H3Si–CH3 Methylsilane | 1J(Si,C) | −54.02 | −55.82 | −54.77 | −58.66 | −55.72 | −54.93 |
1J(Si,H) | −184.74 | −183.56 | −183.57 | −184.81 | −186.05 | −184.78 | ||
2J(Si,H) | 8.30 | 8.96 | 8.42 | 9.27 | 8.59 | 8.53 | ||
16 | H3Si–F Fluorosilane | 1J(Si,H) | −217.11 | −216.95 | −216.31 | −217.40 | −218.39 | −217.41 |
1J(Si,F) | 248.88 | 257.46 | 249.12 | 245.43 | 247.17 | 247.66 | ||
17 | SiH4 Silane | 1J(Si,H) | −191.02 | −190.88 | −190.15 | −192.1 | −192.76 | −191.33 |
18 | F3Si–H Trifluorosilane | 1J(Si,H) | −344.22 | −345.76 | −344.27 | −345.12 | −343.74 | −343.93 |
1J(Si,F) | 239.41 | 252.97 | 241.19 | 243.83 | 238.43 | 237.91 | ||
19 | Silylphosphane | 1J(P,Si) | 6.82 | −5.39 | 4.72 | −3.32 | −1.34 | 4.95 |
1J(P,Hα) | 189.24 | 186.39 | 186.98 | 181.46 | 187.49 | 189.96 | ||
1J(Si,Hβ) | −195.27 | −192.96 | −193.79 | −195.05 | −196.09 | −195.27 | ||
1J(Si,Hγ) | −201.51 | −198.33 | −199.60 | −198.99 | −201.44 | −201.50 | ||
2J(P,Hβ) | 25.41 | 24.92 | 24.84 | 24.42 | 25.00 | 25.27 | ||
2J(P,Hγ) | −5.16 | −3.44 | −4.70 | −4.42 | −5.17 | −5.40 | ||
2J(Si,Hα) | 8.32 | 9.44 | 8.58 | 10.09 | 8.87 | 8.78 | ||
20 | Silylidenephosphane | 1J(P,Si) | 125.09 | 111.02 | 125.27 | 110.88 | 113.64 | 119.58 |
1J(P,Hα) | 135.77 | 132.54 | 133.50 | 126.41 | 130.96 | 136.70 | ||
1J(Si,Hβ) | −227.93 | −223.38 | −224.92 | −227.49 | −227.66 | −227.47 | ||
1J(Si,Hβ’) | −221.37 | −219.50 | −219.69 | −225.64 | −223.94 | −221.05 | ||
2J(P,Hβ) | −31.96 | −29.86 | −31.28 | −31.31 | −32.09 | −32.12 | ||
2J(P,Hβ’) | 36.13 | 34.66 | 35.64 | 35.60 | 35.42 | 36.13 | ||
2J(Si,Hα) | 23.50 | 24.30 | 24.24 | 25.91 | 24.51 | 24.57 |
Basis Set | H | C, N, F | P, Si |
---|---|---|---|
pcJ-1/pcJ-1(uc) | 10/12 | 27/34 | 31/50 |
pecJ-1/pecJ-1(uc) | 11/13 | 27/35 | 38/53 |
pcJ-2/pcJ-2(uc) | 24/27 | 51/62 | 54/77 |
pecJ-2/pecJ-2(uc) | 20/22 | 43/51 | 55/71 |
aug-cc-pVTZ-J/aug-cc-pVTZ-J(uc) | 20/24 | 46/55 | 68/87 |
Molecule | SSCC | Basis Set | CCSD | Δvib 1 | Δrel 2 | Δsol 3 | Jtot | Jexp4 | ||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
JFC | JSD | JPSO | JDSO | Jbasic | ||||||||
1 | 1J(P,C2) | pecJ-1 | −10.14 | 5.09 | −36.72 | 0.20 | −41.57 | −4.33 | −4.91 | 2.95 | −47.86 | (−)53.0 |
pecJ-2 | −12.23 | 5.12 | −37.5 | 0.20 | −44.41 | 3.40 | −50.25 | |||||
2J(P,C3) | pecJ-1 | −13.51 | −3.48 | 0.92 | −0.05 | −16.12 | −1.38 | 0.00 | −0.09 | −17.59 | −14.0 | |
pecJ-2 | −13.56 | −3.42 | 0.93 | −0.05 | −16.10 | −0.26 | −17.74 | |||||
3J(P,C4) | pecJ-1 | 12.57 | 8.81 | 1.67 | −0.04 | 23.01 | 3.39 | −0.24 | 0.55 | 26.71 | 22.0 | |
pecJ-2 | 12.21 | 9.04 | 1.78 | −0.04 | 22.99 | 0.68 | 26.82 | |||||
2J(P,H2) | pecJ-1 | 42.46 | −0.40 | −7.07 | −0.41 | 34.58 | −0.41 | 1.47 | −0.66 | 34.98 | 38.0 | |
pecJ-2 | 43.42 | −0.3 | −7.09 | −0.42 | 35.61 | −0.75 | 35.92 | |||||
3J(P,H3) | pecJ-1 | 8.71 | −0.21 | 0.65 | −0.69 | 8.46 | 0.45 | −0.45 | 0.72 | 9.18 | 8.0 | |
pecJ-2 | 8.58 | −0.28 | 0.70 | −0.70 | 8.30 | 0.77 | 9.07 | |||||
4J(P,H4) | pecJ-1 | −4.33 | −0.29 | 0.55 | −0.64 | −4.71 | −0.69 | 0.32 | −0.03 | −5.11 | −3.5 | |
pecJ-2 | −4.17 | −0.15 | 0.61 | −0.64 | −4.35 | −0.07 | −4.79 | |||||
P≡CH 2 | 1J(P,C) | pecJ-1 | 19.52 | 40.96 | 11.51 | 0.00 | 71.99 | −5.47 | −4.50 | −6.66 | 55.36 | 56.0 |
pecJ-2 | 19.85 | 43.26 | 13.67 | 0.00 | 76.78 | −5.93 | 60.88 | |||||
2J(P,H) | pecJ-1 | 27.88 | 3.28 | 21.48 | −1.46 | 51.18 | −4.16 | 0.24 | 1.37 | 48.63 | 44.0 | |
pecJ-2 | 25.73 | 5.36 | 23.46 | −1.47 | 53.08 | 1.17 | 50.33 | |||||
PH3 8 | 1J(P,H) | pecJ-1 | 179.64 | −0.78 | 5.37 | 0.03 | 184.26 | −9.34 | −2.63 | Gas phase | 172.29 | 176.2 |
pecJ-2 | 182.68 | −0.91 | 5.93 | 0.00 | 187.70 | 175.73 | ||||||
H3Si–F 16 | 1J(Si,H) | pecJ-1 | −215.64 | −0.08 | 1.14 | −0.22 | −214.80 | −8.82 | −3.30 | −1.66 | −228.58 | (−)233.6 |
pecJ-2 | −213.72 | −0.17 | 1.11 | −0.21 | −212.99 | −1.55 | −226.66 | |||||
1J(Si,F) | pecJ-1 | 212.82 | −7.32 | 58.57 | −0.08 | 263.99 | 8.69 | 10.43 | −3.82 | 279.29 | 278.7 | |
pecJ-2 | 203.39 | −7.78 | 58.88 | −0.06 | 254.43 | −3.62 | 269.93 | |||||
SiH4 17 | 1J(Si,H) | pecJ-1 | −189.89 | −0.02 | 0.48 | −0.03 | −189.46 | −7.27 | −2.96 | Gas phase | −199.69 | (−)201.9 |
pecJ-2 | −188.71 | −0.07 | 0.43 | −0.02 | −188.37 | −198.60 |
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Rusakov, Y.Y.; Rusakova, I.L. New pecJ-n (n = 1, 2) Basis Sets for High-Quality Calculations of Indirect Nuclear Spin–Spin Coupling Constants Involving 31P and 29Si: The Advanced PEC Method. Molecules 2022, 27, 6145. https://doi.org/10.3390/molecules27196145
Rusakov YY, Rusakova IL. New pecJ-n (n = 1, 2) Basis Sets for High-Quality Calculations of Indirect Nuclear Spin–Spin Coupling Constants Involving 31P and 29Si: The Advanced PEC Method. Molecules. 2022; 27(19):6145. https://doi.org/10.3390/molecules27196145
Chicago/Turabian StyleRusakov, Yuriy Yu., and Irina L. Rusakova. 2022. "New pecJ-n (n = 1, 2) Basis Sets for High-Quality Calculations of Indirect Nuclear Spin–Spin Coupling Constants Involving 31P and 29Si: The Advanced PEC Method" Molecules 27, no. 19: 6145. https://doi.org/10.3390/molecules27196145