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MOLECULAR-ORBITAL STUDY OF THE CONFORMATIONAL CONSEQUENCES OF STABILIZING AND DESTABILIZING ORBITAL INTERACTIONS IN HYDRAZINE, DIPHOSPHINE, AND AMINOPHOSPHINE
被引:93
作者
:
COWLEY, AH
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV TEXAS, DEPT CHEM, AUSTIN, TX 78712 USA
COWLEY, AH
MITCHELL, DJ
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV TEXAS, DEPT CHEM, AUSTIN, TX 78712 USA
MITCHELL, DJ
WHANGBO, MH
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV TEXAS, DEPT CHEM, AUSTIN, TX 78712 USA
WHANGBO, MH
WOLFE, S
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV TEXAS, DEPT CHEM, AUSTIN, TX 78712 USA
WOLFE, S
机构
:
[1]
UNIV TEXAS, DEPT CHEM, AUSTIN, TX 78712 USA
[2]
QUEENS UNIV, DEPT CHEM, KINGSTON K7L 3N6, ONTARIO, CANADA
[3]
N CAROLINA STATE UNIV, DEPT CHEM, RALEIGH, NC 27650 USA
来源
:
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
|
1979年
/ 101卷
/ 18期
关键词
:
D O I
:
10.1021/ja00512a019
中图分类号
:
O6 [化学];
学科分类号
:
0703 ;
摘要
:
Ab initio SCF-MO calculations have been performed at the 4-31G level for the rotational and pyramidal inversional processes in hydrazine, diphosphine, and aminophosphine. Extensive geometry optimization has been carried out in each case. Combination of the present results with related data from the literature leads to the following conclusions: (1) only the gauche conformation is a minimum on the rotational curve of hydrazine; (2) both gauche and anti conformations are minima on the rotational curve of diphosphine; (3) the dihedral angle in gauche diphosphine is 76° (4) the pyramidal inversion barrier of hydrazine is slightly higher than that of ammonia; (5) the pyramidal inversion barrier of diphosphine is significantly lower than that of phosphine; (6) the “bisected” conformation is the transition state for pyramidal inversion in both hydrazine and diphosphine, but it is the ground state of aminophosphine; (7) nitrogen adopts a pyramidal configuration in the rotational transition state of aminophosphine; (8) the nitrogen inversion barrier is lower in aminophosphine than in ammonia; (9) the phosphorus inversion barrier is higher in aminophosphine than in phosphine. All of these observations are examined by a quantitative perturbational molecular orbital (PMO) analysis of the 4-31G wave functions, which takes into account both the stabilizing two-orbital two-electron and the destabilizing two-orbital four-electron orbital interactions between two AH2fragments or between an AH2and a BH2fragment. Useful insights into the factors responsible for the static and dynamic stereochemical properties of these molecules have thus been achieved. In particular, it has been possible to define, more clearly than in our previous work, the interrelationships between the PMO methodology and more classical concepts such as steric effects, dipoledipole interactions, and electronegativity effects. © 1979, American Chemical Society. All rights reserved.
引用
收藏
页码:5224 / 5231
页数:8
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PAYNE, PW
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UNIV N CAROLINA, DEPT CHEM, CHAPEL HILL, NC 27514 USA
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PEDERSEN, L
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PEDERSEN, L
MOROKUMA, K
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JOURNAL OF CHEMICAL PHYSICS,
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PETTIFOR, DG
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MOLECULAR-ORBITAL THEORY OF ELECTRONIC-STRUCTURE OF ORGANIC COMPOUNDS .13. FOURIER COMPONENT ANALYSIS OF INTERNAL-ROTATION POTENTIAL FUNCTIONS IN SATURATED MOLECULES
RADOM, L
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RADOM, L
POPLE, JA
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HEHRE, WJ
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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,
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SEMIEMPIRICAL CALCULATION OF BARRIERS TO PYRAMIDAL INVERSION FOR FIRST-ROW AND SECOND-ROW ELEMENTS
RAUK, A
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0
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RAUK, A
ANDOSE, JD
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ANDOSE, JD
FRICK, WG
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TANG, R
MISLOW, K
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0
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0
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0
MISLOW, K
[J].
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,
1971,
93
(24)
: 6507
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&
[66]
ROBERT JB, 1970, CHEM COMMUN, P356
[67]
APPROXIMATE RELATION BETWEEN ORBITAL SCF ENERGIES AND TOTAL SCF ENERGY IN MOLECULES
RUEDENBERG, K
论文数:
0
引用数:
0
h-index:
0
机构:
IOWA STATE UNIV,ERDA,AMES LAB,AMES,IA 50011
RUEDENBERG, K
[J].
JOURNAL OF CHEMICAL PHYSICS,
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376
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RELATION BETWEEN ORBITAL SCF ENERGIES AND TOTAL SCF ENERGY IN MOLECULES
SANNIGRAHI, AB
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引用数:
0
h-index:
0
机构:
GARBETA COLL,DEPT CHEM,MIDNAPORE,W BENGAL,INDIA
SANNIGRAHI, AB
DE, BR
论文数:
0
引用数:
0
h-index:
0
机构:
GARBETA COLL,DEPT CHEM,MIDNAPORE,W BENGAL,INDIA
DE, BR
NIYOGI, BG
论文数:
0
引用数:
0
h-index:
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机构:
GARBETA COLL,DEPT CHEM,MIDNAPORE,W BENGAL,INDIA
NIYOGI, BG
[J].
JOURNAL OF CHEMICAL PHYSICS,
1978,
68
(02)
: 784
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[69]
RELATION BETWEEN ORBITAL SCF ENERGIES AND TOTAL SCF ENERGIES IN MOLECULES
SCHAAD, LJ
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0
引用数:
0
h-index:
0
机构:
VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
SCHAAD, LJ
ROBINSON, BH
论文数:
0
引用数:
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h-index:
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机构:
VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
ROBINSON, BH
HESS, BA
论文数:
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引用数:
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VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
HESS, BA
[J].
JOURNAL OF CHEMICAL PHYSICS,
1977,
67
(10)
: 4616
-
4617
[70]
SCHLEGEL HB, 1975, THESIS QUEENS U
←
1
2
3
4
5
6
7
8
9
→
共 83 条
[61]
HARTREE-FOCK THEORY OF LOCAL REGIONS IN MOLECULES
PAYNE, PW
论文数:
0
引用数:
0
h-index:
0
机构:
UNIV N CAROLINA, DEPT CHEM, CHAPEL HILL, NC 27514 USA
PAYNE, PW
[J].
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,
1977,
99
(11)
: 3787
-
3794
[62]
AB INITIO CALCULATIONS OF BARRIERS TO INTERNAL ROTATION OF CH3CH3 CH3NH2 CH3OH N2H4 H2O2 AND NH2OH
PEDERSEN, L
论文数:
0
引用数:
0
h-index:
0
PEDERSEN, L
MOROKUMA, K
论文数:
0
引用数:
0
h-index:
0
MOROKUMA, K
[J].
JOURNAL OF CHEMICAL PHYSICS,
1967,
46
(10)
: 3941
-
&
[63]
INDIVIDUAL ORBITAL CONTRIBUTIONS TO SCF VIRIAL IN HOMONUCLEAR DIATOMIC-MOLECULES
PETTIFOR, DG
论文数:
0
引用数:
0
h-index:
0
PETTIFOR, DG
[J].
JOURNAL OF CHEMICAL PHYSICS,
1978,
69
(06)
: 2930
-
2931
[64]
MOLECULAR-ORBITAL THEORY OF ELECTRONIC-STRUCTURE OF ORGANIC COMPOUNDS .13. FOURIER COMPONENT ANALYSIS OF INTERNAL-ROTATION POTENTIAL FUNCTIONS IN SATURATED MOLECULES
RADOM, L
论文数:
0
引用数:
0
h-index:
0
RADOM, L
POPLE, JA
论文数:
0
引用数:
0
h-index:
0
POPLE, JA
HEHRE, WJ
论文数:
0
引用数:
0
h-index:
0
HEHRE, WJ
[J].
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,
1972,
94
(07)
: 2371
-
&
[65]
SEMIEMPIRICAL CALCULATION OF BARRIERS TO PYRAMIDAL INVERSION FOR FIRST-ROW AND SECOND-ROW ELEMENTS
RAUK, A
论文数:
0
引用数:
0
h-index:
0
RAUK, A
ANDOSE, JD
论文数:
0
引用数:
0
h-index:
0
ANDOSE, JD
FRICK, WG
论文数:
0
引用数:
0
h-index:
0
FRICK, WG
TANG, R
论文数:
0
引用数:
0
h-index:
0
TANG, R
MISLOW, K
论文数:
0
引用数:
0
h-index:
0
MISLOW, K
[J].
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,
1971,
93
(24)
: 6507
-
&
[66]
ROBERT JB, 1970, CHEM COMMUN, P356
[67]
APPROXIMATE RELATION BETWEEN ORBITAL SCF ENERGIES AND TOTAL SCF ENERGY IN MOLECULES
RUEDENBERG, K
论文数:
0
引用数:
0
h-index:
0
机构:
IOWA STATE UNIV,ERDA,AMES LAB,AMES,IA 50011
RUEDENBERG, K
[J].
JOURNAL OF CHEMICAL PHYSICS,
1977,
66
(01)
: 375
-
376
[68]
RELATION BETWEEN ORBITAL SCF ENERGIES AND TOTAL SCF ENERGY IN MOLECULES
SANNIGRAHI, AB
论文数:
0
引用数:
0
h-index:
0
机构:
GARBETA COLL,DEPT CHEM,MIDNAPORE,W BENGAL,INDIA
SANNIGRAHI, AB
DE, BR
论文数:
0
引用数:
0
h-index:
0
机构:
GARBETA COLL,DEPT CHEM,MIDNAPORE,W BENGAL,INDIA
DE, BR
NIYOGI, BG
论文数:
0
引用数:
0
h-index:
0
机构:
GARBETA COLL,DEPT CHEM,MIDNAPORE,W BENGAL,INDIA
NIYOGI, BG
[J].
JOURNAL OF CHEMICAL PHYSICS,
1978,
68
(02)
: 784
-
785
[69]
RELATION BETWEEN ORBITAL SCF ENERGIES AND TOTAL SCF ENERGIES IN MOLECULES
SCHAAD, LJ
论文数:
0
引用数:
0
h-index:
0
机构:
VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
SCHAAD, LJ
ROBINSON, BH
论文数:
0
引用数:
0
h-index:
0
机构:
VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
ROBINSON, BH
HESS, BA
论文数:
0
引用数:
0
h-index:
0
机构:
VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
VANDERBILT UNIV,DEPT CHEM,NASHVILLE,TN 37235
HESS, BA
[J].
JOURNAL OF CHEMICAL PHYSICS,
1977,
67
(10)
: 4616
-
4617
[70]
SCHLEGEL HB, 1975, THESIS QUEENS U
←
1
2
3
4
5
6
7
8
9
→