ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE NEUE FOLGE
|
1990年
/
168卷
关键词:
PHOSPHATES;
CHEMICAL SHIFT;
ATOMIC CHARGES;
SEMIEMPIRICAL THEORY;
D O I:
10.1524/zpch.1990.168.Part_1.115
中图分类号:
O64 [物理化学(理论化学)、化学物理学];
学科分类号:
070304 ;
081704 ;
摘要:
In the first part of the paper a semiempirical formula for the calculation of the P-31-chemical shift is derived from the recently developed bond polarization theory. This formula contains in the case of phosphates only three empirical parameters: (i) the chemical shift of the unpolarized first bond sphere represented by an isolated (PO4)3-, (ii) the chemical shift change with P - O sigma-bond polarization, and (iii) the change with P - O d-p-pi-bond polarization. The last effect is essential for a meaningful description of the phosphorous chemical shift. The three parameters are estimated from a calculation of the bond polarization energies of 18 phosphates. The presented correlation has a mean error of only 2.9 ppm and represents therefore the first quantitative predictive tool for the calculation of chemical shifts of phosphates. The same method can be used for the calculation of atomic charges. Former empirical correlations between structure and chemical shift can be explained using the bond polarization formula.
机构:
Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USAPenn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA
Reed, Titus
Mauro, John C.
论文数: 0引用数: 0
h-index: 0
机构:
Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USAPenn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA
Mauro, John C.
Gevaudan, Juan Pablo
论文数: 0引用数: 0
h-index: 0
机构:
Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA
Penn State Univ, Dept Architectural Engn, University Pk, PA USAPenn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA
Gevaudan, Juan Pablo
INTERNATIONAL JOURNAL OF CERAMIC ENGINEERING AND SCIENCE,
2024,
6
(05):
机构:
Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USAPenn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA
Reed, Titus
Mauro, John C.
论文数: 0引用数: 0
h-index: 0
机构:
Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USAPenn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA
Mauro, John C.
Gevaudan, Juan Pablo
论文数: 0引用数: 0
h-index: 0
机构:
Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA
Penn State Univ, Dept Architectural Engn, University Pk, PA USAPenn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA
Gevaudan, Juan Pablo
INTERNATIONAL JOURNAL OF CERAMIC ENGINEERING AND SCIENCE,
2024,
6
(05):