Optimized geometry, vibration (IR and Raman) spectra and nonlinear optical activity of p-nitroanilinium perchlorate molecule: A theoretical study

Tamer, Ömer; Sefa Atalay, Ahmet; Avci, Davut; Atalay, Yusuf; Tarcan, Erdoğan; Marchewka, Mariusz K.

doi:10.1515/msp-2016-0002

Figures & Tables

(a) Experimental molecular structure, (b) optimized molecular structure of p-nitroanilinium perchlorate obtained at B3LYP/6-311++G(d,p) level.

The comparison of FT-IR and calculated IR spectra for p-nitroanilinium perchlorate.

The comparison of FT-Raman and calculated Raman spectra for p-nitroanilinium perchlorate.

Frontier molecular orbital pictures and energies for p-nitroanilinium perchlorate obtained at B3LYP/6-311++G(d,p).

3D plot of molecular electrostatic potential (MEP) surface for p-nitroanilinium perchlorate obtained at B3LYP/6-311++G(d,p).

3D plot of electrostatic surface potential (ESP) and contour plot of ESP (blue) for p-nitroanilinium perchlorate obtained at B3LYP/6-311++G(d,p) level.

Comparative of Mulliken atomic charges for pnitroanilinium perchlorate obtained at B3LYP and HSEH1PBE levels with 6-311++G(d,p) basis set.

Total static dipol moment (μ, in Debye), the mean polarizability (〈α〉, in 10−24 esu), the anisotropy of the polarizability (∆α, in 10−24 esu), the mean first-order hyperpolarizability (hμi, in 10−30 esu) for p-nitroanilinium perchlorate_

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 [35, 36]
< β > (Urea)	0.13 [37]

The theoretical and experimental N1—H12···O2 and C2—H2···O2 interaction parameters for pnitroanilinium perchlorate_

	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

Second-order perturbation theory analysis of Fock matrix in NBO basic corresponding to the intermolecular bonds for p-nitroanilinium perchlorate_

Donor (i)	Acceptor (j)	E(2) E(2) means energy of hyperconjugative interactions (stabilization energy). (kcal/mol)		E(j)-E(i) Energy difference between donor and acceptor i and j NBO orbitals. (a.u.)		F(i,j) F(i; j) is the Fock matrix element between i and j NBO orbitals. (a.u.)
		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

The frontier orbital energies, electronegativity, hardness and softness for p-nitroanilinium perchlorate_

	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

Experimental and threotical bond lengths for p-nitroanilinium perchlorate_

	XRD [8]	DFT
Bond Lengths (Å)	XRD [8]	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

The selected theoretical and experimental vibration frequencies for p-nitroanilinium perchlorate_

Assignments (B3LYP/6-311++G(d,p) Vibrational modes are based on PED and only contributions over 3 % are given.	Experimental [8]		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.	I_IR IR infrared inten. are in unit of kmμmol⁻¹.	I_R IR Raman activ. are in unit of Å⁴ μamu⁻¹.	Scaled Freq Scaled frequencies are in unit of cm⁻¹.	I_IR IR infrared inten. are in unit of kmμmol⁻¹.	I_R 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

Optimized geometry, vibration (IR and Raman) spectra and nonlinear optical activity of p-nitroanilinium perchlorate molecule: A theoretical study

Figures & Tables

Fig. 1

Fig. 2

Fig. 3

Fig. 4

Fig. 5

Fig. 6

Fig. 7

Total static dipol moment (μ, in Debye), the mean polarizability (〈α〉, in 10−24 esu), the anisotropy of the polarizability (∆α, in 10−24 esu), the mean first-order hyperpolarizability (hμi, in 10−30 esu) for p-nitroanilinium perchlorate_

The theoretical and experimental N1—H12···O2 and C2—H2···O2 interaction parameters for pnitroanilinium perchlorate_

Second-order perturbation theory analysis of Fock matrix in NBO basic corresponding to the intermolecular bonds for p-nitroanilinium perchlorate_

The frontier orbital energies, electronegativity, hardness and softness for p-nitroanilinium perchlorate_

Experimental and threotical bond lengths for p-nitroanilinium perchlorate_

The selected theoretical and experimental vibration frequencies for p-nitroanilinium perchlorate_

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