SUPPLEMENTARY INFORMATION

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1 Capture of Elusive Hydroxymethylene and its Fast Disappearance through Tunnelling Peter R. Schreiner a, Hans Peter Reisenauer a, Frank Pickard b, Andrew C. Simmonett b, Wesley D. Allen b, Edit Mátyus c & Attila G. Császár c a Institut für Organische Chemie der Justus-Liebig-Universität, Heinrich-Buff-Ring 58, D Giessen, Germany. b Center for Computational Chemistry, The University of Georgia, Athens, GA 30602, USA. c Laboratory of Molecular Spectroscopy, Institute of Chemistry, Eötvös University, H-1518 Budapest 112, P.O. Box 32, Hungary. H O H O O 3 HVFP 1000 C Ar, 11 K H CO 2 1 OH O H 2 H 1

2 Supplementary Figures Supplementary Figure 1. Optimized AE-CCSD(T)/cc-pCVQZ geometric structures (Å, deg). 2

3 Supplementary Figure 2. Comparative optimized geometric structures (Å, deg) of the three lowest-lying electronic states of hydroxymethylene. 3

4 Supplementary Tables 1. Experimental Supplementary Table 1. Half-life (in h) of matrix isolated 1t in matrices at different temperatures Temperature/matrix Ar Kr Xe N 2 11 K K 1.9 Not determined Not determined Not determined 20 K Not determined Not determined 2. Computational Supplementary Table 2. Cartesian coordinates (in bohr) of all species optimized at the all-electron(ae) CCSD(T)/cc-pCVQZ level of theory 1c (C s point group) C O H H t (C s point group) H H C O (C 2v point group) C O H H H 2 (D h point group) H H

5 TS2 (C s point group) O C H H TS1 (C 1 point group) H H C O CO (C v point group) C O TS3 (C s point group) O C H H TS4 (C s point group) C O H H Triplet 1 (T 1 state) (C 1 point group) H H C O

6 Supplementary Table 3. Cartesian coordinates (in bohr) of species optimized at the all-electron (AE) Mk-MRCCSD/aug-cc-pCVTZ level of theory 1t (S 0 state) (C s point group) H H C O (S 1 state) (C s point group stationary point) H H C O (S 1 state) (C 1 point group minimum) H C O H

7 Supplementary Table 4. Single-point energies (in hartree) for focal-point extrapolations, computed at the AE-CCSD(T)/cc-pCVQZ optimized geometries. 1c (C s ) cc-pvdz cc-pvtz cc-pvqz cc-pv5z cc-pv6z t (C s ) cc-pvdz cc-pvtz cc-pvqz cc-pv5z cc-pv6z (C 2v ) cc-pvdz cc-pvtz cc-pvqz cc-pv5z cc-pv6z H 2 (D h ) cc-pvdz cc-pvtz cc-pvqz cc-pv5z cc-pv6z TS2 (C s ) cc-pvdz cc-pvtz cc-pvqz cc-pv5z cc-pv6z

8 TS1 (C 1 ) cc-pvdz cc-pvtz cc-pvqz cc-pv5z cc-pv6z CO (C v ) cc-pvdz cc-pvtz cc-pvqz cc-pv5z cc-pv6z TS3 (C s ) cc-pvdz cc-pvtz cc-pvqz cc-pv5z cc-pv6z TS4 (C s ) cc-pvdz cc-pvtz cc-pvqz cc-pv5z cc-pv6z Triplet 1 (T 1 state) (C 1 point group) ROHF CCSD CCSD(T) CCSDT(Q) cc-pvdz cc-pvtz cc-pvqz cc-pv5z cc-pv6z

9 Supplementary Table 5. Focal-point extrapolations of relative energies (all entries in kcal mol 1 ) 1c(C s ) 1t(C s ) ΔE e (HF +δ +δ +δ [CCSD(T)] +δ = ΔE e [CCSDT(Q)] ) (MP2) (CCSD) [CCSDT(Q)] cc-pvdz [+4.60] cc-pvtz [+0.00] [+4.61] cc-pvqz [+0.00] [+4.69] cc-pv5z [+0.00] [+4.77] cc-pv6z [+0.00] [+4.79] [+5.22] [ 0.08] [ 0.22] [ 0.11] [+0.00] [+4.80] Function a+be cx a+bx 3 a+bx 3 a+bx 3 add Fit pts., X = (4, 5, 6) (5, 6) (5, 6) (5, 6) ZPVE (harmonic) = ZPVE (anharmonic) = (core correlation) = (relativity) = (DBOC) = Final E 0 = = (harmonic ZPVE) Final E 0 = = (anharmonic ZPVE) 1t(C s ) 2(C 2v ) ΔE e (HF +δ +δ +δ [CCSD(T)] +δ = ΔE e [CCSDT(Q)] ) (MP2) (CCSD) [CCSDT(Q)] cc-pvdz [+52.29] cc-pvtz [+0.20] [+51.86] cc-pvqz [+0.20] [+52.00] cc-pv5z [+0.20] [+51.96] cc-pv6z [+0.20] [+51.98] [47.81] [+7.93] [ 4.52] [+0.63] [+0.20] [+52.04] Function a+be cx a+bx 3 a+bx 3 a+bx 3 add Fit pts., X = (4, 5, 6) (5, 6) (5, 6) (5, 6) ZPVE (harmonic) = ZPVE (anharmonic) = (core correlation) = (relativity) = (DBOC) = Final E 0 = = (harmonic ZPVE) Final E 0 = = (anharmonic ZPVE) 9

10 H 2 + CO 2(C 2v ) ΔE e (HF +δ +δ +δ [CCSD(T)] +δ = ΔE e [CCSDT(Q)] ) (MP2) (CCSD) [CCSDT(Q)] cc-pvdz [+0.63] cc-pvtz [+0.35] [+4.12] cc-pvqz [+0.35] [+4.94] cc-pv5z [+0.35] [+5.31] cc-pv6z [+0.35] [+5.39] [ 0.64] [+6.38] [ 0.53] [ 0.08] [+0.35] [+5.49] Function a+be cx a+bx 3 a+bx 3 a+bx 3 add Fit pts., X = (4, 5, 6) (5, 6) (5, 6) (5, 6) ZPVE (harmonic) = ZPVE (anharmonic) = (core correlation) = (relativity) = (DBOC) = Final E 0 = = (harmonic ZPVE) Final E 0 = = (anharmonic ZPVE) TS2(C s ) 2(C 2v ) ΔE e (HF +δ +δ +δ [CCSD(T)] +δ = ΔE e [CCSDT(Q)] ) (MP2) (CCSD) [CCSDT(Q)] cc-pvdz [+86.67] cc-pvtz [ 0.28] [+85.84] cc-pvqz [ 0.28] [+85.99] cc-pv5z [ 0.28] [+85.92] cc-pv6z [ 0.28] [+85.89] [98.99] [ 13.00] [+2.78] [ 2.59] [ 0.28] [+85.90] Function a+be cx a+bx 3 a+bx 3 a+bx 3 add Fit pts., X = (4, 5, 6) (5, 6) (5, 6) (5, 6) ZPVE (harmonic) = (core correlation) = (relativity) = (DBOC) = Final E 0 = = (harmonic ZPVE) TS1(C s ) 1t(C s ) ΔE e (HF +δ +δ +δ [CCSD(T)] +δ = ΔE e [CCSDT(Q)] ) (MP2) (CCSD) [CCSDT(Q)] cc-pvdz [+31.66] cc-pvtz [ 0.10] [+30.16] cc-pvqz [ 0.10] [+29.74] cc-pv5z [ 0.10] [+29.52] cc-pv6z [ 0.10] [+29.47] [+26.80] [+4.22] [ 1.88] [+0.36] [ 0.10] [+29.41] Function a+be cx a+bx 3 a+bx 3 a+bx 3 add 10

11 Fit pts., X = (4, 5, 6) (5, 6) (5, 6) (5, 6) ZPVE (harmonic) = (core correlation) = (relativity) = (DBOC) = Final E 0 = = (harmonic ZPVE) TS3(C s ) [H 2 + CO] ΔE e (HF +δ +δ +δ [CCSD(T)] +δ = ΔE e [CCSDT(Q)] ) (MP2) (CCSD) [CCSDT(Q)] cc-pvdz [ ] cc-pvtz [ 0.38] [ ] cc-pvqz [ 0.38] [ ] cc-pv5z [ 0.38] [ ] cc-pv6z [ 0.38] [ ] [122.42] [ 16.91] [+1.31] [ 2.68] [ 0.38] [ ] Function a+be cx a+bx 3 A+bX 3 a+bx 3 add Fit pts., X = (4, 5, 6) (5, 6) (5, 6) (5, 6) ZPVE (harmonic) = (core correlation) = (relativity) = (DBOC) = Final E 0 = = (harmonic ZPVE) Triplet 1(T 1 state, C 1 ) 1t(C s ) ΔE e (HF) +δ (CCSD) +δ [CCSD(T)] +δ = ΔE e [CCSDT(Q)] [CCSDT(Q)] cc-pvdz [+28.56] cc-pvtz [+2.64] [+28.99] cc-pvqz [+2.64] [+29.19] cc-pv5z [+2.64] [+29.27] cc-pv6z [+2.64] [+29.34] [8.89] [+16.32] [+1.56] [+2.64] [+29.41] Function a+be cx a+bx 3 a+bx 3 Add Fit pts., X = (4, 5, 6) (5, 6) (5, 6) ZPVE (harmonic) = 1.31 ZPVE (anharmonic) = 1.29 (core correlation) = 0.28 (relativity) = 0.09 (DBOC) = 0.06 Final E 0 = = (harmonic ZPVE) Final E 0 = = (anharmonic ZPVE) Notation of focal point tables: The symbol δ denotes the increment in the energy difference (ΔE e ) with respect to the previous level of theory. Bracketed numbers are the result of basis set 11

12 extrapolations (using the designated extrapolation functions and fit points), while unbracketed numbers were explicitly computed. The focal-point limits approximate ΔE e [CCSDT(Q)] in the complete basis set limit. Supplementary Table 6. Final focal-point relative energies (kcal mol 1 ) a Species Relative energy CO + H (0.0) H 2 CO (2) 2.3 (2.1) trans-hcoh (1t) 54.2 (54.0) cis-hcoh (1c) 58.6 (58.4) TS TS TS a Values in parentheses include ZPVE anharmonicity. Supplementary Table 7. Total energies (in hartree) computed at the all-electron (AE) Mk-MRCCSD/aug-cc-pCVnZ level. 1 (S 0 state): AE-MkCCSD/aug-cc-pCVnZ//AE-CCSD(T)/cc-pCVQZ (with closed-shell RHF orbitals) Basis set Mk-MRCCSD aug-cc-pcvdz aug-cc-pcvtz aug-cc-pcvqz (S 1 state): AE-MkCCSD/aug-cc-pCVnZ//AE-CCSD(T)/cc-pCVQZ (with triplet RHF orbitals) Basis set Mk-MRCCSD aug-cc-pcvdz aug-cc-pcvtz aug-cc-pcvqz (S 0 state, C s point group): AE-MkCCSD/aug-cc-pCVTZ optimum geometry Total AE-MkCCSD/aug-cc-pCVTZ energy with closed-shell RHF orbitals = E h AE-MkCCSD/aug-cc-pCVTZ harmonic ZPVE = cm 1 1 (S 1 state, C s point group): AE-MkCCSD/aug-cc-pCVTZ optimum geometry Total AE-MkCCSD/aug-cc-pCVTZ energy with triplet RHF orbitals = E h AE-MkCCSD/aug-cc-pCVTZ harmonic ZPVE = cm

13 Supplementary Table 8. AE-CCSD(T)/ccpCVQZ quadratic force constants F ij for trans-h C OH a,b ij F ij ij F ij a F ij units are consistent with energies in aj, distances in Å, and angles in radians. b The force field is represented in the internal coordinates S 1 = ρ CH (r e = Å) S 4 = θ(h C O) S 2 = ρ CO (r e = Å) S 5 = θ(c O H) S 3 = ρ OH (r e = Å) S 6 = τ(h C O H) where the SPF stretching coordinates are ρ = 1 r e /r, r is a bond distance, θ is a valence bond angle, and τ is the backbone dihedral angle. 13

14 Supplementary Table 9. AE-CCSD(T)/ccpCVQZ cubic force constants F ijk for trans- H C OH a ijk F ijk ijk F ijk a See footnotes a and b of Table S

15 Supplementary Table 10. AE-CCSD(T)/cc-pCVQZ quartic force constants F ijkl for trans-h C OH a ijkl F ijkl ijkl F ijkl ijkl F ijkl a See footnotes a and b of Table S

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Electronic Supplementary Information: 2 6 5 7 2 N S 3 9 6 7 5 2 S N 3 9 Scheme S. Atom numbering for thione and thiol tautomers of thioacetamide 3 0.6 0. absorbance 0.2 0.0 0.5 0.0 0.05 0.00 N 2 Ar km/mol