Review of Experimental GAPT and Infrared Atomic Charges in Molecules

Richter, Wagner E.; Duarte, Leonardo J.; Silva, Arnaldo F.; Bruns, Roy E.

doi:10.5935/0103-5053.20160105

person Wagner E. Richter

schoolInstituto de Química, Universidade Estadual de Campinas (Unicamp), CP 6154, 13083-970 Campinas-SP, Brazil Wagner E. Richter received his BSc in Chemistry from State University of Maringá (2010) and his MSc (2013) and PhD (2016) degrees from University of Campinas, working with theoretical aspects of infrared spectroscopy. Currently he is an assistant professor in the Chemistry Department of the State University of Maringá.

person Leonardo J. Duarte

schoolInstituto de Química, Universidade Estadual de Campinas (Unicamp), CP 6154, 13083-970 Campinas-SP, Brazil Leonardo J. Duarte is currently a chemistry undergraduate student at University of Campinas and has an undergraduate research scholarship.

person Arnaldo F. Silva

schoolInstituto de Química, Universidade Estadual de Campinas (Unicamp), CP 6154, 13083-970 Campinas-SP, Brazil Arnaldo F. Silva received a triple major in teaching, technological and Bachelor in Chemistry from State University of Londrina (2008) and his MSc (2011) and PhD (2014) degrees from University of Campinas. He specializes in infrared intensities and theoretical physical chemistry. Currently he is a research collaborator sponsored by FAPESP at the University of Campinas and The University of Manchester.

person Roy E. Bruns *

schoolInstituto de Química, Universidade Estadual de Campinas (Unicamp), CP 6154, 13083-970 Campinas-SP, Brazil Roy E. Bruns received his BA degree from Southern Illinois University in 1963, his PhD from Oklahoma State University in 1968 and did post-doctoral research at the University of Florida with Willis Person. In 1971, he came to Brazil when Unicamp was in its infancy working in quantum chemistry and infrared spectroscopy, focusing on infrared band intensities. He brought the first computer program to Brazil for calculating molecular orbitals. In 1977, he became interested in chemometrics, starting the first course in Brasil on this subject and co-authoring the first book in Portuguese about statistical design of experiments that has sold over 17000 copies. Currently, he is an Emeritus Professor at the University of Campinas continuing work in the above areas appreciating music, beer-drinking and powerlifting.

person*e-mail:
bruns@iqm.unicamp.br

Wagner E. Richter received his BSc in Chemistry from State University of Maringá (2010) and his MSc (2013) and PhD (2016) degrees from University of Campinas, working with theoretical aspects of infrared spectroscopy. Currently he is an assistant professor in the Chemistry Department of the State University of Maringá.

Leonardo J. Duarte is currently a chemistry undergraduate student at University of Campinas and has an undergraduate research scholarship.

Arnaldo F. Silva received a triple major in teaching, technological and Bachelor in Chemistry from State University of Londrina (2008) and his MSc (2011) and PhD (2014) degrees from University of Campinas. He specializes in infrared intensities and theoretical physical chemistry. Currently he is a research collaborator sponsored by FAPESP at the University of Campinas and The University of Manchester.

Roy E. Bruns received his BA degree from Southern Illinois University in 1963, his PhD from Oklahoma State University in 1968 and did post-doctoral research at the University of Florida with Willis Person. In 1971, he came to Brazil when Unicamp was in its infancy working in quantum chemistry and infrared spectroscopy, focusing on infrared band intensities. He brought the first computer program to Brazil for calculating molecular orbitals. In 1977, he became interested in chemometrics, starting the first course in Brasil on this subject and co-authoring the first book in Portuguese about statistical design of experiments that has sold over 17000 copies. Currently, he is an Emeritus Professor at the University of Campinas continuing work in the above areas appreciating music, beer-drinking and powerlifting.

Molecule	Atoma	p _α	β_α	\|χα\|	D_α^1/3	\|C\|_α^1/2	IR charge / e
CH₃F	C	0.550	0.552	0.608	0.497	0.898	-
	F	-0.479	0.605	0.557	-0.408	0.752	-
	H	-0.021	0.191	0.092	-0.042	0.096	-
CH₂F₂	C	1.015	0.644	1.060	0.972	1.719	-
	F	-0.488	0.640	0.574	-0.415		-
	H	-0.018	0.162	0.079	-0.041	0.073	-
CHF₃	C	1.518	0.635	1.548	1.485	2.604	-
	H	-0.003	0.104	0.049	-0.042	0.060	-
	F	-0.505	0.670	0.595	-0.430	0.793	-
CF₄	C	2.051	0.000	2.051	2.051	3.552	-
	F	-0.512	0.410	0.547	-0.472	0.855	-
CH₃Cl	C	0.272	0.491	0.357	0.191	0.376	-
	Cl	-0.268	0.275	0.298	-0.241	0.436	-
	H	-0.001	0.154	0.073	0.010	0.087	-
CH₂Cl₂	C	0.527	0.875	0.669	0.377	0.760	-
	Cl	-0.248	0.412	0.315	-0.193	0.367	-
	H	-0.015	0.124	0.060	0.053	0.065	-
CHCl₃	C	0.823	0.915	0.929	0.647	1.324	-
	H	-0.026	0.086	0.048	0.045	0.020	-
	Cl	-0.265	0.603	0.389	-0.163	0.344	-
CCl₄	C	1.043	0.000	1.043	1.043	1.807	-
	Cl	-0.261	0.398	0.322	-0.158	0.389	-
CH₃Br	C	0.210	0.463	0.303	0.118	0.248	-
	Br	-0.204	0.177	0.220	-0.189	0.338	-
	H	-0.002	0.157	0.070	-0.029	0.090	-
CH₃I	C	0.134	0.341	0.209	0.052	0.122	-
	I	-0.114	0.003	0.114	-0.114	0.197	-
	H	-0.007	0.122	0.075	-0.058	0.066	-
CFCI₃	C	1.367	0.120	1.368	1.366	2.367	-
	F	-0.486	0.602	0.563	-0.416	0.766	-
	Cl	-0.294	0.662	0.428	-0.148	0.356	-
CF₂CI₂	C	1.636	0.433	1.649	1.623	2.823	-
	F	-0.585	0.653	0.661	-0.516	0.940	-
	Cl	-0.233	0.562	0.353	0.225	0.251	-
CF₃CI	C	2.033	0.680	2.058	2.009	3.499	-
	Cl	-0.148	0.725	0.544	-0.244	0.602	-
	F	-0.629	0.741	0.719	-0.540	1.001	-
F₂CO	C	1.514	1.469	1.664	1.292	2.480	0.53
	O	-0.554	0.477	0.598	-0.509	0.918	-0.31
	F	-0.484	0.786	0.610	-0.339	0.702	-0.11
Cl₂CO	C	1.243	1.612	1.457	0.849	1.942	0.20
	O	-0.587	0.677	0.667	-0.486	0.939	-0.20
	Cl	-0.337	0.829	0.516	0.000	0.340	0.00
F₂CS	C	1.175	1.620	1.401	0.759	1.807	0.12
	S	-0.257	0.577	0.374	-0.131	0.294	-0.04
	F	-0.450	0.904	0.620	-0.224	0.580	-0.04
Cl₂CS	C	0.893	1.586	1.165	-0.677	1.248	-0.15
	S	-0.295	0.716	0.449	0.171	0.296	0.04
	Cl	-0.298	0.853	0.501	0.175	0.178	0.06
Br₂CO	C	1.027	1.399	1.220	0.604	1.584	0.10
	O	-0.700	0.829	0.802	-0.537	1.114	-0.17
	Br	-0.160	0.431	0.259	0.121	0.153	0.04
H₂CO	C	0.575	0.571	0.636	0.497	0.938	0.16
	O	-0.477	0.409	0.515	-0.439	0.790	-0.33
	H	-0.052	0.243	0.126	0.036	0.100	0.08
cis-C₂H₂F₂	C	0.313	0.964	0.552	-0.149	0.105	-0.063
	H	0.059	0.182	0.104	-0.053	0.042	0.159
	F	-0.372	0.853	0.548	-0.206	0.435	-0.096
cis-C₂H₂Cl₂	C	0.160	0.952	0.476	0.246	0.449	-0.106
	H	0.047	0.171	0.093	-0.063	0.052	0.147
	Cl	-0.206	0.579	0.342	-0.071	0.180	-0.041
1,1-C₂H₂F₂	C₁	-0.274	0.276	0.303	-0.231	0.446	-0.329
	C₂	0.977	1.224	1.134	0.676	1.537	0.161
	H	0.072	0.314	0.164	-0.109	0.026	0.162
	F	-0.423	0.913	0.604	-0.243	0.525	-0.078
CH₄	C	0.015	0.000	0.015	0.015	0.026	-
	H	-0.004	0.167	0.079	-0.028	0.095	-
C₂H₄	C	0.011	0.385	0.189	-0.168	0.222	-0.246
	H	-0.006	0.197	0.093	0.082	0.112	0.122
C₂H₆	C	0.064	0.171	0.103	-0.090	0.050	-
	H	-0.021	0.223	0.107	-0.075	0.123	-
C₃H₄ (propyne)	H₇	0.198	0.026	0.199	0.198	0.343	-
	C₆	-0.313	0.186	0.325	-0.302	0.531	-
	H₁	0.048	0.138	0.139	-0.056	0.076	-
	C4	0.097	0.071	0.103	0.090	0.164	-
C₃H₄ (allene)	C₁	0.032	0.822	0.389	0.324	0.471	-
	C₃	-0.132	0.449	0.250	0.234	0.121	-
	H	0.058	0.161	0.096	0.043	0.061	-
C₃H₆ (cyclopropane)	C	0.017	0.269	0.128	-0.121	0.152	-
	H	-0.009	0.170	0.081	0.377	0.091	-
C₆H₆	C	-0.027	0.199	0.098	0.091	0.105	-0.119
	H	0.027	0.199	0.098	-0.091	0.105	0.119
C₄H₆ (butyne)	C₄	0.117	0.090	0.124	0.107	0.196	-
	H	0.002	0.186	0.088	0.067	0.098	-
	Q	-0.124	0.149	0.143	-0.091	0.197	-
C₂H₂	H	0.20,	0.018	0.201	0.200	0.347	0.205
	C	-0.201	0.018	0.201	-0.200	0.347	-0.205
HCN	H	0.231	0.019	0.231	0.230	0.399	0.237
	C	-0.041	0.376	0.182	-0.127	0.204	0.084
	N	-0.189	0.395	0.266	0.197	0.236	-0.321
CO₂	O	-0.536	0.901	0.684	-0.399	0.770	-0.236
	C	1.073	1.802	1.368	0.797	1.539	0.472
CS₂	S	-0.344	1.284	0.696	-0.204	0.441	0.084
	C	0.688	2.568	1.392	0.408	0.882	-0.168
OCS	O	-0.581	1.433	0.891	-0.254	0.572	-0.103
	S	-0.268	0.811	0.467	0.015	0.057	0.002
	C	0.849	2.244	1.356	0.288	0.696	0.101
N₁NO	N₁	-0.281	0.518	0.372	-0.194	0.383	-0.108
	O	-0.505	1.098	0.723	-0.288	0.603	-0.139
	N	0.786	1.616	1.094	0.484	0.991	0.247
ClCN	Cl	-0.037	0.574	0.273	-0.215	0.325	0.154
	N	-0.202	0.157	0.215	-0.184	0.337	-0.254
	C	0.243	0.424	0.308	0.165	0.324	0.093
BrCN	Br	0.070	0.369	0.188	-0.187	0.175	0.193
	N	-0.192	0.102	0.198	-0.185	0.327	-0.226
	C	0.122	0.267	0.175	0.069	0.145	0.033
SiH₄	Si	0.918	0.000	0.918	0.918	1.590	-
	H	-0.229	0.119	0.235	-0.222	0.390	-
SiH₄	Si	0.904	0.000	0.904	0.904	1.566	-
	H	-0.226	0.026	0.226	-0.226	0.392	-
GeH₄	Ge	0.862	0.000	0.862	0.862	1.493	-
	H	-0.216	0.068	0.218	-0.214	0.372	-
SnH₄	Sn	1.016	0.000	1.016	1.016	1.760	-
	H	-0.254	0.081	0.257	-0.251	0.437	-
SiF₄	SÍ	2.215	0.000	2.215	2.215	3.836	-
	H	-0.554	0.121	0.557	-0.551	0.957	-
C₂H₃N	C₁	0.110	0.102	0.120	0.096	0.181	-
	H₁	0.034	0.127	0.069	-0.028	0.031	-
	C₂	0.067	0.017	0.067	0.066	0.115	-
	N	-0.278	0.160	0.288	-0.266	0.472	-
H₂O	O	-0.472	0.312	0.494	-0.448	0.797	-0.658
	H	0.236	0.198	0.254	0.234	0.404	0.329
C₆F₆	C	0.428	0.957	0.621	0.215	0.494	0.057
	F	-0.428	1.044	0.653	-0.188	0.432	-0.057
NH₃	N	-0.101	0.634	0.316	-0.185	0.321	-
	H	0.034	0.356	0.171	0.039	0.064	-
PH₃	P	0.357	0.116	0.361	0.353	0.614	-
	H	-0.119	0.120	0.132	-0.107	0.194	-
NF₃	N	1.154	0.838	1.219	1.069	1.939	-
	F	-0.385	0.695	0.505	-0.312	0.596	-
PF₃	P	1.740	0.251	1.744	1.736	3.011	-
	F	-0.580	1.052	0.763	-0.430	0.834	-
BF₃	B	1.517	1.030	1.592	1.421	2.559	0.83
	F	-0.507	0.485	0.556	-0.459	0.832	-0.28
BCl₃	B	0.747	0.940	0.868	0.513	1.174	0.12
	Cl	-0.247	0.465	0.330	-0.149	0.332	-0.04
C₂H₄O	O	-0.483	0.157	0.286	0.280	0.481	-
	H	-0.018	0.184	0.089	0.014	0.079	-
	C	0.277	0.098	0.385	0.379	0.660	-
C₂N₂	N	-0.122	0.368	0.212	0.197	0.017	-0.245
	C	0.122	0.368	0.212	-0.197	0.017	0.245
SO₂	O	-0.504	0.700	0.602	-0.435	0.825	-0.235
	S	1.016	1.125	1.140	0.887	1.641	0.471
HF	H	0.382	0.098	0.385	0.379	0.660	0.415
	F	-0.382	0.098	0.385	-0.379	0.660	-0.415
HCl	H	0.184	0.014	0.184	0.184	0.318	0.179
	Cl	-0.184	0.014	0.184	-0.184	0.318	-0.179
HBr	H	0.114	0.021	0.114	0.114	0.197	0.121
	Br	-0.114	0.021	0.114	-0.114	0.197	-0.121
HI	H	0.040	0.044	0.045	0.032	0.065	0.055
	I	-0.040	0.044	0.045	-0.032	0.065	-0.055
LiH	H	-0.654	0.271	0.666	-0.640	1.121	-0.747
	Li	0.654	0.271	0.666	0.640	1.121	0.747
CO	O	-0.228	0.751	0.421	-0.071	0.178	0.022
	C	0.228	0.751	0.421	0.071	0.178	-0.022
LiF	F	-0.861	0.071	0.861	-0.860	1.490	-0.837
	Li	0.861	0.071	0.861	0.860	1.490	0.837
LiCl	Cl	-0.760	0.090	0.761	-0.759	1.315	-0.730
	Li	0.760	0.090	0.761	0.759	1.315	0.730
NaF	F	-0.889	0.032	0.889	-0.889	1.539	-0.878
	Na	0.889	0.032	0.889	0.889	1.539	0.878
NaCl	Cl	-0.809	0.053	0.809	-0.808	1.400	-0.791
	Na	0.809	0.053	0.809	0.808	1.400	0.791
KCl	Cl	-0.830	0.092	0.830	-0.829	1.436	-0.799
	K	0.830	0.092	0.830	0.829	1.436	0.799
NO	O	-0.151	0.541	0.297	-0.076	0.170	0.029
	N	0.151	0.541	0.297	0.076	0.170	-0.029

Molecule	APT (experimental) / e	CSSM (transferred) / e
CH₂F₂	1.015	1.085
CHF₃	1.518	1.620
CF₄	2.015	2.155
CH₂Cl₂	0.527	0.559
CHCl₃	0.823	0.831
CCl₄	1.043	1.103
CFCl₃	1.367	1.366
CF₂Cl₂	1.636	1.629
CF₃Cl	2.033	1.892
OCS	0.849	0.881
Cl₂CS	0.893	0.904

Molecule	E_(1s,C) / eV	E_(rel) / eV	V_(CHELPG) / eV	V_(Mulliken) / eV	V_{(zero flux)} / eV	V_(GAPT) / eV
CH4	290.9	-14.26	4.343	4.858	-0.18	-0.13
CH₃F	293.6	-13.97	-1.735	-0.671	-6.66	-5.78
CH₂F₂	296.36	-13.62	-4.870	-4.370	-13.77	-10.93
CHF₃	299.1	-13.25	-7.078	-6.496	-21.66	-16.41
CF₄	301.85	-12.92	-9.424	-7.991	-30.48	-22.45
CH₃Cl	292.48	14.75	2.686	3.002	-0.4448	-2.19
CH₂Cl₂	293.9	-15.17	2.382	1.331	-11.749	-4.47
CHCl₃	295.1	-15.56	1.838	-0.363	-23.104	-6.77
CCI₄	296.39	-15.95	2.395	-1.620	-37.862	-8.49
CCl₃F	297.54	-15.44	0.240	-3.855	-10.359	-12.42
CCI₂F₂	298.93	-14.78	-1.523	-5.608	-17.047	-16.43
CClF₃	300.31	-13.95	-4.623	-6.960	-23.735	-21.71

[TFN1] ^a
The subindices in the atom column identify nonequivalent multiple atoms in the molecules. p_α: mean dipole moment derivative; β_α: square root of the anisotropy; |χα|: absolute value of the effective charge; D_α^1/3: cubic root of the determinant; and |C|_α^1/2: square root of the absolute value of the sum of cofactors.

Review of Experimental GAPT and Infrared Atomic Charges in Molecules

Abstract