According to the nonequilibrium solvation theory studies, a constrained equilibrium principle is introduced and applied to the derivations of the nonequilibrium solvation energy, and a reasonable expression of the spe...According to the nonequilibrium solvation theory studies, a constrained equilibrium principle is introduced and applied to the derivations of the nonequilibrium solvation energy, and a reasonable expression of the spectral shift of the electronic absorption spectra is deduced. Furthermore, the lowest transition of p-nitroaniline （pNA） in water is investigated by time-dependent density functional theory method. In addition, the details of excited state properties of pNA are discussed. Using our novel expression of the spectral shift, the value of -0.99 eV is obtained for π→π^＊ transition in water, which is in good agreement with the available experimental result of -0.98 eV.展开更多
The 304 nm photodissociation of the C-H symmetric stretch excited CH3I[v1=1,v2=0](v1 denotes the C-H symmetric stretch mode,and v2 denotes the umbrella mode)is studied with our simple photofragment translational spect...The 304 nm photodissociation of the C-H symmetric stretch excited CH3I[v1=1,v2=0](v1 denotes the C-H symmetric stretch mode,and v2 denotes the umbrella mode)is studied with our simple photofragment translational spectrometer.An IR laser is used to excite the ground state CH3I[0,0]to the C-H symmetric stretch excited CH3I[1,0].With IR laser OFF and ON,the fractions of photofragments CH3(ν1,ν2)from the 304 nm photodissociation of CH3I[1,0]have been determined through the photofragment translational spectra(PTS)from measuring I and I*and also through the PTS from measuring CH3(0,0)(1,0)(0,1)and(1,1).The experimental results show that the C-H symmetric stretch vibration(v1=1)in parent molecules is about 66%retained in the photofragments in the I channel,but only 24%in the I*channel.The populations of photofragments CH3(0,2)and(0,3)are higher than CH3(0,0)and(0,1),showing strong inverted population both in I and I*channels.展开更多
基金ACKNOWLEDGMENTS This work was supported Science Foundation of China by the National Natural （No.91016002）.
文摘According to the nonequilibrium solvation theory studies, a constrained equilibrium principle is introduced and applied to the derivations of the nonequilibrium solvation energy, and a reasonable expression of the spectral shift of the electronic absorption spectra is deduced. Furthermore, the lowest transition of p-nitroaniline （pNA） in water is investigated by time-dependent density functional theory method. In addition, the details of excited state properties of pNA are discussed. Using our novel expression of the spectral shift, the value of -0.99 eV is obtained for π→π^＊ transition in water, which is in good agreement with the available experimental result of -0.98 eV.
基金supported by the National Natural Science Foundation of China(21203207 and 21173236)
文摘The 304 nm photodissociation of the C-H symmetric stretch excited CH3I[v1=1,v2=0](v1 denotes the C-H symmetric stretch mode,and v2 denotes the umbrella mode)is studied with our simple photofragment translational spectrometer.An IR laser is used to excite the ground state CH3I[0,0]to the C-H symmetric stretch excited CH3I[1,0].With IR laser OFF and ON,the fractions of photofragments CH3(ν1,ν2)from the 304 nm photodissociation of CH3I[1,0]have been determined through the photofragment translational spectra(PTS)from measuring I and I*and also through the PTS from measuring CH3(0,0)(1,0)(0,1)and(1,1).The experimental results show that the C-H symmetric stretch vibration(v1=1)in parent molecules is about 66%retained in the photofragments in the I channel,but only 24%in the I*channel.The populations of photofragments CH3(0,2)and(0,3)are higher than CH3(0,0)and(0,1),showing strong inverted population both in I and I*channels.
