Nonequilibrium Solvation Theory Based on Constrained Equilibrium Principle and Its Applications†

doi:10.7503/cjcu20150645

Abstract

Abstract:

A novel nonequilibrium solvation theory established recently by the authors was introduced. Differing from the traditional ones, the present theory was based on the constrained equilibrium principle of classical thermodynamics. The calculations of solvent reorganization energy were performed with the electron transfer system of Np $O 2 +$ -Np $O 2 2 +$ as an example. The constrained density functional theory was adopted for the charge localization of the system and IEF-PCM was used for the gain of polarization charges in water. Both two-sphere model and numerical solution give consistent and reasonable solvent reorganization energies.

Key words: Nonequilibrium solvation, Constrained equilibrium state, Electron transfer, Solvent reorganization energy

CLC Number:

O641

TrendMD:

MING Meijun, BI Tingjun, LI Xiangyuan. Nonequilibrium Solvation Theory Based on Constrained Equilibrium Principle and Its Applications^†[J]. Chem. J. Chinese Universities, 2015, 36(11): 2256.

Figures/Tables 3

Table 1 Total energies, bond lengths and Mulliken charges on atoms for species NpO2m+(m=1,2) in gas and solution phase(in parentheses)

Species	E_tot/(kJ·mol^-1)		d(Np=O)/nm		q(Np)/e		q(O)/e
Species	Calcd.	Ref.[21]	Calcd.	Ref.[21]	Calcd.	Ref.[21]	Calcd.	Ref.[21]
Np $O 2 +$	-554663(-555222)	-554565(-555168)	0.174(0.181)	0.174(0.179)	1.68(2.00)	1.68(2.20)	-0.34(-0.50)	-0.34(-0.60)
Np $O 2 2 +$	-552978(-554485)	-553005(-554509)	0.172(0.176)	0.171(0.175)	2.06(2.56)	2.02(2.50)	-0.03(-0.28)	-0.01(-0.25)

Table 1 Total energies, bond lengths and Mulliken charges on atoms for species NpO2m+(m=1,2) in gas and solution phase(in parentheses)

Species	E_tot/(kJ·mol^-1)		d(Np=O)/nm		q(Np)/e		q(O)/e
Species	Calcd.	Ref.[21]	Calcd.	Ref.[21]	Calcd.	Ref.[21]	Calcd.	Ref.[21]
Np $O 2 +$	-554663(-555222)	-554565(-555168)	0.174(0.181)	0.174(0.179)	1.68(2.00)	1.68(2.20)	-0.34(-0.50)	-0.34(-0.60)
Np $O 2 2 +$	-552978(-554485)	-553005(-554509)	0.172(0.176)	0.171(0.175)	2.06(2.56)	2.02(2.50)	-0.03(-0.28)	-0.01(-0.25)

Fig.1 Geometries of precursor(A) and transition state(B) of self-exchange NpO2++NpO22+ NpO22++NpO2+ in water

Table 2 Solvent reorganization energy and activation energy by two-sphere model and numerical solution

Species	$R 1 *$ /nm	$R 2 *$ /nm	$λ s$	$λ$	ΔG^*/(kJ·mol^-1)	$Δ G * (Expt)$ ^[26]/(kJ·mol^-1)
Eq(M)^[23]	0.432	0.439	82.1	164.4	41.1	34.7
Eq(M)	0.292	0.309	160.9	242.4	60.8
Eq(Li)	0.292	0.309	83.0	165.3	41.3
Numerical			102.9	185.6	46.4

Table 2 Solvent reorganization energy and activation energy by two-sphere model and numerical solution

Species	$R 1 *$ /nm	$R 2 *$ /nm	$λ s$	$λ$	ΔG^*/(kJ·mol^-1)	$Δ G * (Expt)$ ^[26]/(kJ·mol^-1)
Eq(M)^[23]	0.432	0.439	82.1	164.4	41.1	34.7
Eq(M)	0.292	0.309	160.9	242.4	60.8
Eq(Li)	0.292	0.309	83.0	165.3	41.3
Numerical			102.9	185.6	46.4

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