Bendkowsky Vera, Heinecke Elke, Hese Achim
Institut für Optik und Atomare Physik, Technische Universität Berlin, Hardenbergstr. 36, 10623 Berlin, Germany.
J Chem Phys. 2007 Dec 14;127(22):224306. doi: 10.1063/1.2806184.
We present rotationally resolved spectra of the S(1)<--S(0) transition of anthracene at 27,687.153(4) cm(-1) as well as Stark effect measurements of the free anthracene molecule in electric fields of up to 85 kV/cm. The molecule is rotationally cooled in a supersonic jet expansion to a temperature of 4 K. The rotational constants of the electronic states S(0) and S(1) are determined by a simplex fit comparing the experimental spectra with simulations for an asymmetric rigid rotor. The measured and simulated energies are in very good agreement and the estimated accuracy of the rotational constants is 1 per thousand. Furthermore, the polarizabilities of the electronic states S(0) and S(1) are investigated. At an electric field of 85 kV/cm, line shifts of up to 150 MHz caused by a change in the polarizability of Deltaalpha=123(7) a.u. and broadenings due to the anisotropy are observed. The components of the tensor polarizabilities of the electronic states S(0) and S(1) are determined by simulating the complete spectra using second-order perturbation theory.
我们给出了蒽在27,687.153(4) cm⁻¹处S(1)←S(0)跃迁的转动分辨光谱,以及在高达85 kV/cm电场中对自由蒽分子的斯塔克效应测量结果。该分子在超声速喷射膨胀中被转动冷却至4 K的温度。通过将实验光谱与非对称刚性转子的模拟结果进行单纯形拟合,确定了电子态S(0)和S(1)的转动常数。测量值与模拟值非常吻合,转动常数的估计精度为千分之一。此外,还研究了电子态S(0)和S(1)的极化率。在85 kV/cm的电场下,观察到由于极化率变化Δα = 123(7) a.u.导致的高达150 MHz的谱线位移以及由于各向异性引起的展宽。通过使用二阶微扰理论模拟完整光谱,确定了电子态S(0)和S(1)的张量极化率分量。