Collisional deactivation of vibrationally highly excited azulene in compressed liquids and supercritical fluids
Collisional deactivation of vibrationally highly excited azulene in compressed liquids and supercritical fluids
复制标题
压缩液体和超临界流体中振动高度激发的甘菊环的碰撞失活
DOI：
10.1063/1.472180
复制
发表时间：
1996
影响因子：
4.4
通讯作者：
M. Zerezke
中科院分区：
文献类型：
--
作者：
D. Schwarzer;J. Troe;M. Votsmeier;M. Zerezke
The collisional deactivation of vibrationally highly excited azulene was studied from the gas to the compressed liquid phase. Employing supercritical fluids like He, Xe, CO2, and ethane at pressures of 6–4000 bar and temperatures ≥380 K, measurements over the complete gas–liquid transition were performed. Azulene with an energy of 18 000 cm−1 was generated by laser excitation into the S1 and internal conversion to the S0*‐ground state. The subsequent loss of vibrational energy was monitored by transient absorption at the red edge of the S3←S0 absorption band near 290 nm. Transient signals were converted into energy‐time profiles using hot band absorption coefficients from shock wave experiments for calibration and accounting for solvent shifts of the spectra. Under all conditions, the decays were monoexponential. At densities below 1 mol/l, collisional deactivation rates increased linearly with fluid density. Average energies 〈ΔE〉 transferred per collision agreed with data from dilute gas phase experiment...
