Property | B3LYP/6-311++G(d,p) | HSEH1PBE/6-311++G(d,p) |
---|---|---|
μx | –4.940 | –4.911 |
μy | 5.288 | 5.277 |
μz | –0.318 | –0.313 |
µ | 7.244 | 7.216 |
αxx | 26.782 | 26.077 |
αyy | 19.729 | 19.336 |
αzz | 11.703 | 11.349 |
< α > | 19.405 | 18.921 |
Dα | 48.193 | 46.937 |
βxxx | –11.267 | –10.218 |
βyyy | 0.177 | 0.138 |
βzzz | 0.265 | 0.120 |
< β > | 11.272 | 10.220 |
< β > (pNA) | 14.39 [ | |
< β > (Urea) | 0.13 [ |
D—H···A | D—H (Å) | H···A (Å) | D ···A (Å) | D—H···A (°) | |
---|---|---|---|---|---|
XRD | N1—H12···O2 | 0.793(14) | 2.242(14) | 2.9992(14) | 160.0(13) |
C2—H2···O2 | 0.829 | 2.642 | 3.262 | 132.7 | |
B3LYP | N1—H12···O2 | 1.058 | 1.718 | 2.660 | 145.5 |
N1—H13···O3 | 1.058 | 1.718 | 2.660 | 145.5 | |
C2—H2···O1 | 1.085 | 2.413 | 3.469 | 162.3 | |
HSEH1PBE | N1—H12···O2 | 1.063 | 1.662 | 2.662 | 147.3 |
N1—H13···O3 | 1.056 | 1.714 | 2.641 | 143.7 | |
C2—H2···O1 | 1.087 | 2.338 | 3.393 | 163.2 |
Donor (i) | Acceptor (j) | E(2) E(2) means energy of hyperconjugative interactions (stabilization energy). | E(j)-E(i) Energy difference between donor and acceptor i and j NBO orbitals. | F(i,j) F(i; j) is the Fock matrix element between i and j NBO orbitals. | |||
---|---|---|---|---|---|---|---|
B3LYP | HSEH1PBE | B3LYP | HSEH1PBE | B3LYP | HSEH1PBE | ||
σ (C1-C6) | σ*. (C1-C2) | 4.34 | 4.55 | 1.29 | 1.30 | 0.067 | 0.069 |
σ (C1-C6) | σ* (C5-C6) | 2.88 | 3.05 | 1.30 | 1.31 | 0.55 | 0.057 |
π (C1-C6) | π* (C2-C3) | 17.30 | 16.26 | 0.31 | 0.31 | 0.066 | 0.064 |
π (C1-C6) | π* (C4-C5) | 19.99 | 18.88 | 0.30 | 0.30 | 0.070 | 0.067 |
σ (C4-C5) | σ* (C3-C4) | 4.64 | 4.91 | 1.29 | 1.30 | 0.069 | 0.071 |
σ (C4-C5) | σ* (C5-C6) | 2.56 | 2.71 | 1.29 | 1.30 | 0.051 | 0.053 |
π (C4-C5) | π* (C1-C6) | 19.13 | 17.97 | 0.28 | 0.27 | 0.065 | 0.063 |
π (C4-C5) | π* (C5-C6) | 20.61 | 19.61 | 0.30 | 0.29 | 0.071 | 0.069 |
π (C4-C5) | π* (N2-O5) | 24.48 | 21.51 | 0.15 | 0.16 | 0.059 | 0.059 |
LP(3) O6 | π* (N2-O5) | 164.96 | 161.35 | 0.14 | 0.15 | 0.139 | 0.139 |
LP(3) O2 | σ* (N1-H12) | 19.61 | 13.49 | 0.62 | 0.56 | 0.100 | 0.078 |
LP(3) O3 | σ* (N1-H13) | 19.65 | 19.14 | 0.62 | 0.75 | 0.101 | 0.109 |
B3LYP/6-311++G(d,p) | HSEH1PBE/6-311++G(d,p) | |
---|---|---|
EHOMO (eV) | –8.2281 | –8.1285 |
ELUMO (eV) | –3.6830 | –3.7505 |
DE | 4.5451 | 4.3780 |
χ (eV) | 5.9555 | 5.9395 |
η (eV) | 2.2725 | 2.1890 |
S (eV−1) | 0.2200 | 0.2284 |
XRD [8] | DFT | ||
---|---|---|---|
Bond Lengths (Å) | B3LYP | HSEH1PBE | |
Cl1-/O1 | 1.4355(9) | 1.4815 | 1.4638 |
Cl1-/O2 | 1.4419(9) | 1.5329 | 1.5138 |
Cl1-/O3 | 1.4420(9) | 1.5329 | 1.5094 |
Cl1-/O4 | 1.4133(9) | 1.4607 | 1.4441 |
C1-/N1 | 1.4703(13) | 1.4635 | 1.4518 |
N2-/C4 | 1.4756(15) | 1.4851 | 1.4747 |
N2-/O5 | 1.2147(15) | 1.2229 | 1.2134 |
N2-/O6 | 1.2092(14) | 1.2213 | 1.2119 |
N1-/H11 | 0.879(16) | 1.058 | 1.063 |
N1-/H12 | 0.793(14) | 1.018 | 1.016 |
N1-/H13 | 0.901(15) | 1.058 | 1.056 |
C1-/C2 | 1.3601(17) | 1.3927 | 1.3895 |
C2-/C3 | 1.3762(18) | 1.3907 | 1.3868 |
C3-/C4 | 1.3713(18) | 1.3903 | 1.3865 |
C4-/C5 | 1.3588(18) | 1.3890 | 1.3851 |
C5-/C6 | 1.3812(17) | 1.3905 | 1.3866 |
C1-/C6 | 1.3661(16) | 1.3905 | 1.3873 |
C1-/C6 | 1.3661(16) | 1.3905 | 1.3873 |
C2-/H2 | 0.829(11) | 1.085 | 1.087 |
C4-/C3-/H3 | 121.8(9) | 119.866 | 119.714 |
C3-/H3 | 0.926(14) | 1.081 | 1.082 |
C5-/H5 | 0.867(12) | 1.080 | 1.082 |
C6-/H6 | 0.926(13) | 1.084 | 1.085 |
R2 | 0.9524 | 0.9548 | |
Bond Angles (◦) | |||
O2-/Cl1-/O4 | 109.99(6) | 110.311 | 110.410 |
O3-/Cl1-/O4 | 110.72(6) | 110.312 | 110.122 |
O5-/N2-/O6 | 123.49(11) | 125.309 | 125.535 |
O6-/N2-/C4 | 118.43(10) | 117.395 | 117.283 |
O5-/N2-/C4 | 118.05(11) | 117.295 | 117.181 |
N2-/C4-/C3 | 118.68(11) | 118.993 | 118.960 |
N2-/C4-/C5 | 119.16(11) | 118.631 | 118.567 |
C3-/C4-/C5 | 122.14(11) | 122.376 | 122.472 |
C4-/C5-/H5 | 121.2(8) | 119.913 | 119.743 |
C6-/C5-/H5 | 120.1(8) | 121.543 | 171.757 |
C4-/C5-/C6 | 118.72(12) | 118.544 | 118.495 |
C5-/C6-/C1 | 119.37(12) | 119.251 | 119.235 |
H6-/C6-C1 | 118.8(8) | 120.906 | 120.856 |
C6-/C1-/C2 | 121.56(11) | 122.124 | 122.160 |
C6-/C1-/N1 | 119.53(10) | 119.446 | 119.511 |
C2-/C1-/N1 | 118.88(10) | 118.430 | 118.329 |
C4-/C3-/C2 | 118.71(12) | 119.101 | 119.073 |
C4-/C3-/C2 | 118.71(12) | 119.101 | 119.073 |
H3-/C3-/C2 | 119.4(9) | 121.033 | 121.214 |
C3-/C2-/C1 | 119.47(12) | 118.604 | 118.566 |
C1-/C2-/H2 | 123.3(8) | 121.075 | 121.041 |
C3-/C2-/H2 | 117.2(8) | 120.321 | 120.393 |
C1-/N1-/H12 | 114.7(10) | 113.128 | 112.919 |
C1-/N1-/H11 | 110.0(10) | 112.639 | 112.793 |
C1-/N1-/H13 | 110.8(10) | 113.127 | 112.904 |
H12-/N1-/H13 | 109.5(13) | 109.788 | 110.235 |
H12-/N1-/H11 | 106.0(14) | 109.790 | 110.117 |
H13-/N1-/H11 | 105.3(13) | 97.372 | 96.811 |
R2 | 0.8674 | 0.8588 |
Assignments (B3LYP/6-311++G(d,p) Vibrational modes are based on PED and only contributions over 3 % are given. | Experimental [ | B3LYP/6-311++G(d,p) | HSEH1PBE/6-311++G(d,p) | |||||
---|---|---|---|---|---|---|---|---|
FT-IR | FT-Raman | Scaled Freq Scaled frequencies are in unit of cm−1. | IIR IR infrared inten. are in unit of kmμmol−1. | IR IR Raman activ. are in unit of Å4 μamu−1. | Scaled Freq Scaled frequencies are in unit of cm−1. | IIR IR infrared inten. are in unit of kmμmol−1. | IR IR Raman activ. are in unit of Å4 μamu−1. | |
ν NH 84 | 3155 | 3381 | 59.42 | 66.00 | 3423 | 65.27 | 64.82 | |
ν CH 80 | 3135 | 3102 | 8.46 | 28.55 | 3120 | 9.11 | 48.29 | |
ν CH 81 | 3103 | 3101 | 6.36 | 109.61 | 3119 | 7.25 | 90.54 | |
ν CH 77 | 3089 | 3090 | 3053 | 4.10 | 85.65 | 3075 | 2.99 | 86.25 |
ν CH 72 | 3029 | 3049 | 54.22 | 114.18 | 3055 | 70.88 | 116.42 | |
ν N—H····O 80 | 2712 | 2703 | 2849 | 1693.79 | 481.98 | 2872 | 1469.67 | 386.53 |
ν N—H···O 78 | 2646 | 2722 | 146.04 | 19.59 | 2700 | 417.37 | 68.16 | |
ν CC 12 + β NH3 32 | 1605 | 1640 | 1606 | 61.92 | 12.01 | 1641 | 85.74 | 1.13 |
ν CC 10 + β NH3 29 | 1591 | 1589 | 229.50 | 17.63 | 1613 | 142.67 | 59.71 | |
ν NO2 43 | 1496 | 1576 | 59.47 | 94.53 | 1597 | 238.16 | 64.33 | |
β HNH 69 | 1539 | 1538 | 1550 | 22.55 | 3.89 | 1579 | 125.16 | 25.92 |
β CNH 6 + β N—H···O 37 | 1425 | 1539 | 422.80 | 57.07 | 1545 | 21.12 | 3.83 | |
β CNH 7 + β N—H···O 43 | 1375 | 1523 | 305.43 | 65.26 | 1528 | 496.23 | 81.48 | |
ν CC 64 | 1468 | 1470 | 73.80 | 3.08 | 1482 | 85.13 | 3.80 | |
ν CC 45 | 1433 | 1432 | 1411 | 5.25 | 0.88 | 1424 | 5.42 | 0.63 |
ν NO2 44 + ν NC 13 + ν CC 10 | 1241 | 1320 | 289.36 | 212.00 | 1374 | 324.96 | 212.03 | |
ν CC 32 + β HCC 26 | 1312 | 1310 | 1308 | 47.29 | 7.08 | 1342 | 38.25 | 2.26 |
β HCC 49 + β HNC 6 | 1297 | 1298 | 1288 | 4.89 | 0.48 | 1285 | 1.95 | 0.46 |
ν CC 13 + ν NC 20 | 1203 | 1204 | 1174 | 24.23 | 56.56 | 1200 | 16.75 | 62.64 |
ν CC 15 + ν NC 6 + β HCC 62 | 1183 | 1183 | 1163 | 3.23 | 5.74 | 1167 | 8.02 | 5.15 |
β HCC 30 | 1139 | 1101 | 6.84 | 3.14 | 1123 | 443.92 | 11.72 | |
β HCC 22 + ν NC 10 | 1121 | 1120 | 1074 | 16.18 | 66.37 | 1102 | 6.79 | 2.14 |
β CCC 13 + β HCC 19 | 1113 | 1111 | 1056 | 117.48 | 3.63 | 1094 | 47.15 | 48.10 |
ν ClO 5 + β CNH 8 | 1077 | 1047 | 339.25 | 6.57 | 1058 | 31.99 | 0.52 | |
ν ClO 7 + β CNH 8 | 1052 | 1052 | 1032 | 0.20 | 2.76 | 1041 | 2.64 | 2.92 |
β CNH 7 + γ N—H···O 32 | 980 | 992 | 6.14 | 0.57 | 1012 | 353.55 | 3.20 | |
γ CCCC 8 + γ HCCC 47 + γ HCCN 7 | 980 | 0.19 | 0.01 | 994 | 25.77 | 0.56 | ||
ν ClO 38 | 928 | 928 | 944 | 330.79 | 3.37 | 984 | 1.50 | 0.01 |
γ HCCH 16 + γ CCCC 15 + γ HCCC 30 + γ HCCN 16 | 943 | 0.66 | 0.05 | 946 | 0.06 | 0.04 | ||
γ HCCC 82 + γ CCCC 10 | 850 | 849 | 93.65 | 0.43 | 871 | 270.07 | 0.082 | |
γ CCCC 14 + β NO2 34 | 863 | 864 | 841 | 37.26 | 21.72 | 860 | 36.31 | 24.98 |
γ HCCC 40 + γ NCCH 22 + γ CCNH 9 | 831 | 809 | 116.94 | 0.49 | 838 | 33.15 | 0.45 | |
γ HCCC 25 + γ NCCH 12 | 822 | 794 | 83.55 | 0.31 | 813 | 129.19 | 50.19 | |
γ CCCC 42 | 792 | 793 | 777 | 31.60 | 7.76 | 805 | 2.23 | 0.49 |
γ NO2 51 | 739 | 741 | 749 | 104.24 | 51.85 | 788 | 18.51 | 3.15 |
γ CCNO 42 + γ CCCC 19 | 722 | 704 | 4.38 | 1.68 | 714 | 9.49 | 1.56 | |
γ CCNO 24 + γ CCCC 20 | 680 | 662 | 18.38 | 0.03 | 670 | 15.98 | 0.09 |