Journal of Chemistry

Research Article

NLO and NBO Analysis of Sarcosine-Maleic Acid by Using HF and B3LYP Calculations

Table 4

(a) Second-order perturbation theory analysis of Fock matrix on NBO basis for sarcosine-maleic acid by using the HF and B3LYP methods with 6-31++G(d,p) basis set. (b) Second-order perturbation theory analysis of Fock matrix on NBO basis for sarcosine-maleic acid by using the HF and B3LYP methods with 6-31G(d,p) basis set.

(a)


Donor (i)	Occupancies		Acceptor (j)	Occupancies		E(2)^a (kcal/mol)		(a.u.)		(a.u.)
Donor (i)	HF	B3LYP		HF	B3LYP	HF	B3LYP	HF	B3LYP	HF	B3LYP

σ (H₁₀–C₆)	1.976	1.971	σ * (H₉–C₅)	0.009	0.011	0.87	0.63	1.48	1.00	0.032	0.023
σ (H₁₀–C₆)	1.976	1.971	σ * (C₇–O₅)	0.067	0.088	5.86	5.13	1.43	0.92	0.083	0.062
σ (H₁₀–C₆)	1.976	1.971	σ * (C₆–C₅)	0.014	0.017	2.53	1.49	1.68	1.16	0.058	0.037
σ (H₁₀–C₆)	1.976	1.971	σ * (C₅–C₄)	0.065	0.065	8.54	7.49	1.38	0.93	0.098	0.075
σ (H₉–C₅)	1.977	1.972	σ * (C₇–C₆)	0.063	0.076	8.69	7.03	1.37	0.92	0.098	0.073
σ (H₉–C₅)	1.977	1.972	σ * (C₆–C₅)	0.014	0.017	2.47	1.66	1.68	1.16	0.058	0.039
σ (O₆–C₇)	1.983	1.996	σ * (C₇–C₆)	0.063	0.076	0.85	0.77	2.07	1.45	0.038	0.030
σ (O₆–C₇)	1.983	1.996	σ * (O₅–H₁₁)	0.054	0.060	1.43	1.10	2.20	1.51	0.051	0.037
π (O₆–C₇)	1.983	1.968	π * (C₆–C₅)	0.027	0.052	6.46	6.67	0.74	0.39	0.062	0.046
σ (C₇–C₆)	1.985	1.986	σ * (H₉–C₅)	0.009	0.011	2.34	1.81	1.65	1.14	0.056	0.041
σ (C₇–C₆)	1.985	1.986	σ * (C₆–C₅)	0.014	0.017	2.41	1.65	1.84	1.31	0.060	0.041
π (C₆–C₅)	1.921	1.876	π * (O₆–C₇)	0.185	0.249	17.06	1.07	0.61	1.38	0.094	0.034
π (C₆–C₅)	1.921	1.876	π * (C₄–O₃)	0.257	0.265	18.03	1.60	0.58	1.35	0.096	0.041
σ (C₄–O₃)	1.996	1.996	σ * (C₆–C₅)	0.014	0.017	1.26	1.14	2.34	1.71	0.049	0.040
σ (C₄–O₃)	1.996	1.996	σ * (C₅–C₄)	0.065	0.065	0.66	1.04	2.04	1.48	0.033	0.035
π (C₄–O₃)	1.985	1.975	π * (C₆–C₅)	0.027	0.052	5.14	5.51	0.75	0.41	0.056	0.043
π (C₄–O₃)	1.985	1.975	π * (C₄–O₃)	0.257	0.265	0.71	0.71	0.71	0.38	0.022	0.016
σ (C₄–O₃)	1.985	1.996	σ * (C₆–C₅)	0.014	0.017	52.66	1.14	0.03	1.71	0.098	0.040
σ (C₅–C₄)	1.982	1.982	σ * (H₁₀–C₆)	0.008	0.010	2.34	1.56	1.65	1.17	0.056	0.038
σ (C₅–C₄)	1.982	1.982	σ * (C₆–C₅)	0.014	0.017	2.27	1.82	1.84	1.32	0.058	0.044
σ (O₅–H₁₁)	1.986	1.984	σ * (O₆–C₇)	0.015	0.249	7.88	6.39	2.00	1.37	0.112	0.084
σ (C₃–N₁)	1.993	1.993	σ _* (C₂–C₁)	0.057	0.065	1.20	1.22	1.58	1.08	0.039	0.033
σ (C₃–H₇)	1.992	1.991	σ * (C₂–N₁)	0.011	0.013	3.73	3.18	1.28	0.85	0.062	0.046
σ (C₃–H₈)	1.994	1.992	σ * (H₅–N₁)	0.017	0.018	2.81	2.25	1.40	0.94	0.056	0.041
σ (C₂–C₁)	1.981	1.979	σ * (C₁–O₂)	0.020	0.024	0.74	0.55	1.84	1.26	0.033	0.024
σ (C₂–H₃)	1.979	1.969	π * (C₁–O₂)	0.162	0.218	6.89	5.90	0.95	0.52	0.075	0.052
σ (C₂–H₃)	1.979	1.969	σ * (C₁–O₂)	0.020	0.024	1.43	1.56	1.69	1.12	0.044	0.037
σ (C₂–H₂)	1.981	1.971	σ * (H₅–N₁)	0.017	0.018	2.56	2.00	1.40	0.95	0.053	0.039
σ (C₂–N₁)	1.990	1.989	σ * (C₃–H₇)	0.003	0.005	1.04	0.91	1.69	1.18	0.043	0.029
σ (C₂–N₁)	1.990	1.989	σ * (C₁–O₁)	0.069	0.093	2.44	2.23	1.66	1.08	0.058	0.045
σ (H₅–N₁)	1.987	1.986	σ * (C₂–C₁)	0.057	0.065	0.82	0.73	1.50	1.00	0.032	0.024
σ (H₅–N₁)	1.987	1.986	σ * (C₂–H₂)	0.008	0.019	1.00	1.54	1.29	1.09	0.032	0.037
σ (H₅–N₁)	1.987	1.986	σ * (C₃–H₈)	0.004	0.009	2.14	1.71	1.60	1.09	0.052	0.039
π (C₁–O₂)	1.993	1.992	σ * (C₂–H₂)	0.008	0.019	1.00	0.85	1.29	0.85	0.032	0.024
σ (C₁–O₂)	1.993	1.997	σ *(C₂–C₁)	0.057	0.065	0.80	0.83	2.06	1.46	0.059	0.032
σ (C₁–O₂)	1.993	1.997	σ *(C₂–H₃)	0.009	0.019	1.29	1.21	1.24	0.81	0.036	0.028
σ (C₁–O₁)	1.996	1.997	σ * (C₂–N₁)	0.011	0.013	1.13	1.10	1.82	1.28	0.041	0.034
σ (O₁–H₁)	1.987	1.986	σ * (C₂–C₁)	0.057	0.065	6.59	4.58	1.63	1.12	0.093	0.065
σ (O₁–H₁)	1.987	1.986	σ * (C₁–O₂)	0.020	0.024	0.77	0.63	1.97	1.35	0.035	0.026
LP1 (O₂)	1.975	1.976	σ * (C₂–C₁)	0.057	0.065	3.11	2.58	1.56	1.08	0.063	0.048
LP2 (O₂)	1.879	1.848	σ * (C₂–C₁)	0.057	0.065	27.82	19.08	1.06	0.64	0.156	0.101
π * (C₁–O₂)	0.020	0.218	σ * (C₂–H₃)	0.009	0.019	1.04	0.90	0.48	0.42	0.068	0.051
π * (C₁–O₂)	0.020	0.218	σ * (C₂–H₂)	0.008	0.018	0.57	0.53	0.53	0.46	0.053	0.041

(b)


Donor (i)	Occupancies		Acceptor (j)	Occupancies		E(2)^a (kcal/mol)		(a.u.)		(a.u.)
Donor (i)	HF	B3LYP		HF	B3LYP	HF	B3LYP	HF	B3LYP	HF	B3LYP

σ (H₁₀–C₆)	1.980	1.971	σ * (O₆–C₇)	0.016	0.019	1.11	0.55	1.40	1.19	0.035	0.023
σ (H₁₀–C₆)	1.980	1.971	σ * (C₇–O₅)	0.026	0.089	8.07	0.61	1.65	1.14	0.103	0.024
σ (H₁₀–C₆)	1.980	1.971	σ * (C₆–C₅)	0.018	0.017	1.09	1.69	1.56	1.17	0.037	0.040
σ (H₁₀-C₆)	1.980	1.971	σ * (C₅–C₄)	0.033	0.065	4.64	7.88	1.54	0.93	0.076	0.077
σ (H₉–C₅)	1.980	1.972	σ * (C₇–C₆)	0.043	0.075	3.72	7.46	1.57	0.92	0.069	0.075
σ (H₉–C₅)	1.980	1.972	σ * (C₆–C₅)	0.018	0.017	1.42	1.87	1.56	1.17	0.042	0.042
σ (O₆–C₇)	1.991	1.996	σ * (C₅–C₆)	0.015	0.017	3.63	1.04	1.72	1.78	0.071	0.038
σ (O₆–C₇)	1.991	1.996	σ * (O₅–H₁₁)	0.113	0.063	0.69	1.61	1.75	1.60	0.032	0.046
π (O₆–C₇)	1.945	1.967	π * (C₆–C₅)	0.069	0.054	15.39	6.96	0.53	0.39	0.081	0.047
σ (C₇–C₆)	1.989	1.988	σ * (H₉–C₅)	0.010	0.012	3.30	2.28	1.68	1.15	0.066	0.046
σ (C₇–C₆)	1.989	1.988	σ * (C₆–C₅)	0.018	0.017	2.05	2.10	1.80	1.31	0.054	0.047
π (C₆–C₅)	1.833	1.877	π * (O₆–C₇)	0.379	0.250	26.74	13.31	0.53	0.31	0.113	0.060
π (C₆–C₅)	1.833	1.877	σ * (C₄–O₃)	0.035	0.021	18.46	17.31	0.59	0.29	0.097	0.066
σ (C₄–O₃)	1.988	1.997	σ * (C₆–C₅)	0.018	0.017	3.33	1.01	1.79	1.72	0.069	0.037
σ (C₄–O₃)	1.988	1.997	σ * (C₅–C₄)	0.033	0.065	0.80	1.11	2.06	1.49	0.037	0.037
π (C₄–O₃)	1.988	1.975	π * (C₆–C₅)	0.069	0.054	5.52	5.84	0.75	0.41	0.058	0.044
π (C₄–O₃)	1.988	1.975	σ * (C₄–O₃)	0.035	0.021	0.66	0.70	0.72	0.38	0.021	0.016
σ (C₄–O₃)	1.988	1.997	σ * (C₆–C₅)	0.018	0.017	3.33	1.01	1.79	1.72	0.069	0.037
σ (C₅–C₄)	1.989	1.981	σ * (H₁₀–C₆)	0.001	0.011	2.60	1.74	1.72	1.16	0.060	0.040
σ (C₅–C₄)	1.989	1.981	σ * (C₆–C₅)	0.018	0.017	2.22	2.32	1.83	1.33	0.057	0.050
σ (O₅–H₁₁)	1.985	1.985	σ * (O₆–C₇)	0.044	0.250	7.75	6.06	2.00	1.38	0.111	0.082
σ (C₃–H₈)	1.991	1.995	σ * (C₂–N₁)	0.014	0.017	4.77	3.81	1.27	0.84	0.069	0.051
σ (C₃–H₆)	1.992	1.992	σ * (H₅–N₁)	0.010	0.024	3.40	2.73	1.47	0.97	0.063	0.046
σ (C₃–N₁)	1.991	1.992	σ * (C₂–C₁)	0.039	0.075	2.93	1.57	1.54	1.06	0.060	0.037
σ (C₂–C₁)	1.989	1.989	σ * (C₁–O₂)	0.018	0.024	0.86	0.62	1.83	1.26	0.036	0.025
σ (C₂–H₃)	1.975	1.977	π * (C₁–O₂)	0.148	0.207	6.31	3.35	0.88	0.56	0.069	0.041
σ (C₂–H₃)	1.975	1.977	σ * (C₁–O₂)	0.018	0.024	2.53	2.35	1.69	1.14	0.058	0.046
σ (C₂–H₂)	1.982	1.971	σ * (C₁–O₂)	0.146	0.024	1.85	1.40	1.69	1.14	0.050	0.036
σ (C₂–N₁)	1.989	1.988	σ * (C₃–H₈)	0.006	0.010	1.14	0.99	1.75	1.22	0.040	0.031
σ (C₂–N₁)	1.989	1.988	σ * (C₁–O₁)	0.050	0.094	2.25	2.32	1.51	1.09	0.052	0.046
σ (H₅–N₁)	1.988	1.982	σ * (C₂–C₁)	0.039	0.075	0.70	0.58	1.46	0.97	0.029	0.022
σ (H₅–N₁)	1.988	1.982	σ * (C₂–H₃)	0.010	0.018	2.42	2.17	1.58	1.05	0.055	0.043
σ (H₅–N₁)	1.988	1.982	σ * (C₃–H₆)	0.005	0.009	2.56	2.13	1.60	1.08	0.057	0.043
π (C₁–O₂)	1.992	1.992	σ * (C₂–H₂)	0.009	0.023	0.84	1.21	1.16	0.81	0.028	0.028
σ (C₁–O₂)	1.993	1.996	σ *(C₂–C₁)	0.039	0.075	0.69	0.68	2.02	1.42	0.034	0.028
σ (C₁–O₂)	1.993	1.996	σ * (C₂–H₃)	0.009	0.018	1.37	1.14	1.29	0.82	0.037	0.027
σ (C₁–O₁)	1.995	1.996	σ * (C₂–N₁)	0.012	0.017	1.11	0.83	1.62	1.28	0.038	0.029
σ (O₁–H₁)	1.987	1.985	σ * (C₁–O₂)	0.018	0.024	5.50	5.84	1.55	1.36	0.082	0.080
LP1 (O₂)	1.986	1.977	σ * (C₂–C₁)	0.039	0.075	2.99	2.69	1.60	1.03	0.062	0.048
LP2 (O₂)	1.929	1.833	σ * (C₂–C₁)	0.039	0.075	9.82	20.44	0.98	0.61	0.088	0.102
π * (C₁–O₂)	0.148	0.207	σ * (C₂–H₃)	0.009	0.018	0.78	0.63	0.61	0.40	0.070	0.043
π * (C₁–O₂)	0.148	0.207	σ * (C₂–H₂)	0.009	0.023	0.70	0.63	0.46	0.40	0.058	0.043

^aE(2) means energy of hyperconjugative interactions (stabilization energy).
^b Energy difference between donor and acceptor i and j NBO orbitals.
^cF(i, j) is the Fock matrix element between i and j NBO orbital.
LP(n)A is a valence lone pair orbital (n) on A atom.