Supporting information for
Water assisted isomerization of the [H, C, N, O] system
Jia Cao[(], Zhixiang Wang, Loujun Gao, Feng Fu
College of Chemistry & Chemical engineering, Yan’an University, Shaanxi 716000, China
Theory of AIM and ELF
The topology analysis technique is proposed by Bader. In topology analysis language, the points at where gradient norm of function value is zero (except at infinity) are called as critical points (CPs), CPs can be classified into four types bond critical point (bcp), ring critical point (rcp), cage critical point (ccp) and nuclear critical point (ncp). Take the bond critical point (bcp) for example, topological properties of a bond are characterized by the existence of a bond critical point (bcp) and the values of the electron density (r) and its Laplacian (Ñ2r) at the bond critical point. Ñ2r<0 indicates that the density is locally concentrated and characterizes a covalent bond. Ñ2r>0 indicates that the density is locally depleted and characterizes closed-shell interactions as found in ionic bonds, hydrogen bonds, dative bonds, and van der Waals interactions. The strength of the bond can be estimated from the magnitude of the electron density (rbcp) at the bcp. These values of electron density and its Laplacian are well within the range specified for the existence of the hydrogen bond in terms of electron density (0.002-0.040au) and its Laplacian (0.024-0.139 au). Similarly, the ring structure is characterized by the existence of a ring critical point. [Phys. Chem. Chem. Phys. 12 (2010) 2116; J. Phys. Chem. A 113 (2009), 5633; Chem. Phys. Lett. 551 (2012) 31; Int. J. Quantum. Chem 114 (2014) 1239; Struct Chem (2015) 26:261–268].
Becke and Edgecombe introduced the electron location function (ELF), defined so as to have the convenient range of values 0~1. The larger the electron localization is in a region, the more likely the electron motion is confined within. Regions in which the values of ELF is close to 1 corresponding to well-localized electrons, and may be identified with atomic shells, chemical bonds and lon electron pairs [Phys. Chem. Chem. Phys. 2014, 16, 6726; Angew. Chem. Int. Engl. 30 (1991): 409].
Fig. S1. Optimized geometries of all the species at the M06-2X/6–311+G(3df,2p) level Bond lengths are in Å and angles are in °. The values in parentheses are calculated in the water solution by PCM at the M06-2X/6–311+G(3df,2p) level. a denote the experiment data [26,27].
Fig.S2 The distribution of the molecular electrostatic potential of all the isomers at the M06-2X/6–311+G(3df,2p) level of theory.
Fig.S3. ELF maps of species in the isomerization from HNCO to HOCN at M06-2X/6–311+G(3df,2p) level. Regions of the greatest and smallest localization electron density are assigned to be red and blue, respectively. The redder area (greater localization electron density) is considered where the two nuclei interact with each other more favorable, and vice versa.
Fig.S4. ELF maps of species in the isomerization form HCON to HNOC at M06-2X/6–311+G(3df,2p) level. Regions of the greatest and smallest localization electron density are assigned to be red and blue, respectively. The redder area (greater localization electron density) is considered where the two nuclei interact with each other more favorable, and vice versa.
Table S1 The zero point energies (ZPE), electronic energies (E), total energies (ET), relative energies (ER) to the reactants (HCNO+nH2O, n=0-3) in the gas phase (in kcal·mol-1).
Species / ZPEa / Eb / ETc / ERH2O / 0.021676 / -76.3316734 / -76.3099974
HCNO / 0.020095 / -168.3225546 / -168.3024596
HONC / 0.021054 / -168.3004467 / -168.2793927 / 14.47
cycl-NCO(H) / 0.020112 / -168.2574027 / -168.2372907 / 40.89
Y-OC(H)N / 0.020283 / -168.2941228 / -168.2738398 / 17.96
HOCN / 0.022079 / -168.3947742 / -168.3726952 / -44.07
HNCO / 0.021593 / -168.4344707 / -168.4128777 / -69.29
cycl-OCN(H)-a / 0.020356 / -168.2631597 / -168.2428037 / 37.43
cycl-OCN(H)-b / 0.020349 / -168.263181 / -168.242832 / 37.42
HCON / 0.018651 / -168.1763944 / -168.1577434 / 90.81
HNOC / 0.018141 / -168.2204677 / -168.2023267 / 62.83
IM1 / 0.045226 / -244.6614094 / -244.6161834 / -2.34
IM2 / 0.046477 / -244.649548 / -244.603071 / 5.89
IM3 / 0.070835 / -321.0080466 / -320.9372116 / -9.26
IM4 / 0.072146 / -321.000932 / -320.928786 / -3.97
IM5 / 0.09694 / -397.3589973 / -397.2620573 / -18.58
IM6 / 0.097533 / -397.3511956 / -397.2536626 / -13.31
IM7 / 0.04579 / -244.7725358 / -244.7267458 / -71.72
IM8 / 0.047589 / -244.7448542 / -244.6972652 / -53.22
IM9 / 0.072339 / -321.1212012 / -321.0488622 / -79.32
IM10 / 0.073116 / -321.0985064 / -321.0253904 / -64.59
IM11 / 0.097673 / -397.4707707 / -397.3730977 / -88.26
IM12 / 0.097932 / -397.4493137 / -397.3513817 / -74.63
IM13 / 0.043454 / -244.5136323 / -244.4701783 / 89.28
IM14 / 0.042233 / -244.5580705 / -244.5158375 / 60.63
IM15 / 0.069129 / -320.8596012 / -320.7904722 / 82.82
IM16 / 0.0681 / -320.8997777 / -320.8316777 / 56.96
IM17 / 0.094881 / -397.208104 / -397.113223 / 74.82
IM18 / 0.092289 / -397.2467414 / -397.1544524 / 48.95
TS1 / 0.016095 / -168.210848 / -168.194753 / 67.59
TS2 / 0.016476 / -168.2083071 / -168.1918311 / 69.42
TS3 / 0.017736 / -168.2634672 / -168.2457312 / 35.60
TS4 / 0.015676 / -168.1000174 / -168.0843414 / 136.87
TS5 / 0.015332 / -168.2056038 / -168.1902718 / 70.40
TS6 / 0.014879 / -168.1897851 / -168.1749061 / 80.04
TS7 / 0.019106 / -168.2562677 / -168.2371617 / 40.98
TS8 / 0.0187 / -168.2518062 / -168.2331062 / 43.52
TS9 / 0.016192 / -168.2845336 / -168.2683416 / 21.41
TS10 / 0.014301 / -168.2021725 / -168.1878715 / 71.91
TS11 / 0.017391 / -168.2239346 / -168.2065436 / 60.19
TS12 / 0.014228 / -168.0234356 / -168.0092076 / 184.02
TS6-1W / 0.069519 / -244.5952029 / -244.5256839 / 54.45
TS6-2W / 0.069519 / -320.9716597 / -320.9021407 / 12.75
TS6-3W / 0.093114 / -397.3253644 / -397.2322504 / 0.13
TS9-1W / 0.045639 / -244.7083239 / -244.6626849 / -31.52
TS9-2W / 0.069615 / -321.082869 / -321.013254 / -56.98
TS9-3W / 0.09429 / -397.4360177 / -397.3417277 / -68.57
TS12-1W / 0.041603 / -244.4530214 / -244.4114184 / 126.15
TS12-2W / 0.066424 / -320.8247092 / -320.7582852 / 103.02
TS12-3W / 0.09156 / -397.1777894 / -397.0862294 / 91.76
a at the M06-2X/6-311+G(3df,2p) level of theory
b at the CCSD(T)/6-311+G(3df,2p) level of theory
c at the CCSD(T)/6-311++G(3df,2p)//M06-2X/6-311+G(3df,2p)+ZPE level of theory
Table S2 The zero point energies (ZPE), electronic energies (E), total energies (ET), relative energies (ER) to the energy of the HCNO in water solution (in kcal·mol-1).
Species / ZPEa / Eb / ETc / ERHCNO / 0.0210800 / -168.3290909 / -168.3080109 / 0.00
HONC / 0.0210920 / -168.3093265 / -168.2882345 / 12.41
cycl-NCO(H) / 0.0201590 / -168.2637937 / -168.2436347 / 40.40
Y-OC(H)N / 0.0203120 / -168.3011651 / -168.2808531 / 17.04
HOCN / 0.0219340 / -168.4060644 / -168.3841304 / -47.77
HNCO / 0.0212870 / -168.4393402 / -168.4180532 / -69.05
cycl-OCN(H)-a / 0.0203020 / -168.2678132 / -168.2475112 / 37.96
cycl-OCN(H)-b / 0.0203020 / -168.2678142 / -168.2475122 / 37.96
HCON / 0.0185650 / -168.1783934 / -168.1598284 / 92.99
HNOC / 0.0182010 / -168.2265250 / -168.2083240 / 62.55
TS1 / 0.017041 / -168.2245425 / -168.2075015 / 63.07
TS2 / 0.017004 / -168.2245369 / -168.2075329 / 63.05
TS3 / 0.017795 / -168.2691733 / -168.2513783 / 35.54
TS4 / 0.015653 / -168.1028858 / -168.0872328 / 138.54
TS5 / 0.015152 / -168.2086616 / -168.1935096 / 71.85
TS6 / 0.0145780 / -168.1953623 / -168.1807843 / 79.84
TS7 / 0.019063 / -168.2618788 / -168.2428158 / 40.91
TS8 / 0.018622 / -168.2576077 / -168.2389857 / 43.31
TS9 / 0.0159090 / -168.2910322 / -168.2751232 / 20.64
TS10 / 0.014129 / -168.2058332 / -168.1917042 / 72.98
TS11 / 0.017209 / -168.2279537 / -168.2107447 / 61.04
TS12 / 0.0137610 / -168.0251757 / -168.0114147 / 186.12
a at the PCM-M06-2X /6-311+G(3df,2p) level of theory
b at the PCM-CCSD(T) /6-311+G(3df,2p) level of theory
c at the PCM-CCSD(T)/6-311++G(3df,2p)//M06-2X/6-311+G(3df,2p)+ZPE level of theory
Table S3 Natural charges on the leaving C atom for the isomerization of HCNO to HONC from the M06-2X/6-311+G(3df,2p) calculations
Charges / C / CTS-CHCNOHCNO / -0.0406
TS6 / 0.3079 / 0.3485
TS6-1W / -0.1331 / -0.0925
TS6-2W / -0.1111 / -0.0705
TS6-3W / -0.0884 / -0.0478
Table S4 Natural charges on the leaving N atom for the isomerization of HNCO to HOCN from the M06-2X/6-311+G(3df,2p) calculations
Charges / N / NTS-NHNCOHNCO / -0.7923
TS9 / -0.4273 / 0.3650
TS9-1W / -0.6900 / 0.1023
TS9-2W / -0.7244 / 0.0679
TS9-3W / -0.7324 / 0.0599
Table S5 Natural charges on the leaving N atom for the isomerization of HCON to HNOC from the M06-2X/6-311+G(3df,2p) calculations
Charges / N / NTS-NHCONHCON / -0.0336
TS12 / -0.4433 / -0.4097
TS12-1W / -0.4398 / -0.4063
TS12-2W / -0.4321 / -0.3985
TS12-3W / -0.4312 / -0.3976
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