The lowest free molecule rydberg transition of naphthalene
The lowest free molecule rydberg transition of naphthalene
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萘的最低自由分子里德伯跃迁
DOI：
10.1071/ch9710173
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发表时间：
1971
期刊：
影响因子：
--
通讯作者：
G. C. Morris
中科院分区：
文献类型：
--
作者：
J. Angus;G. C. Morris
The absorption spectrum of the naphthalene moleculel92 at energies from 50000 cm-1 to 66000 cm-1 is explicable in terms of (a) extravalence transitions to Rydberg states,(b) intravalence transitions to higher r* states,(c) effects arising from interference between resonance and potential scattering. 3 Line-widths of the absorption bands provide a criterion for distinguishing the extravalence and intravalence transitions. The efficient intramolecular electronic relaxation operative in the higher lying intravalence excitations give rise to diffuse absorption bands usually one or two orders of magnitude broader than the isoenergetic Rydberg bands. The bands of the Rydberg system have energies (F cm-1) given by where. Ip is the ionization potential of the molecule (65620h40 cm-I), R is the Rydberg constant, n the principal quantum number, and 6 the quantum defect. Previously we have identified bands beginning with n= 4 but have been unable to identify the lowest n= 3 Rydberg state. With the current interest in the description of impurity states of a matrix (eg benzene or naphthalene in rare gas solids) 4-6 it is important to know the transition energy of the lowest free molecule Rydberg state. Thus, while Wannier impurity states of naphthalene-rare gas matrices have been observed, 4 there is uncertainty about the existence of an impurity state which might derive its parentage from the lowest Rydberg state of the isolated molecule.In Figure 1 is shown the absorption spectra between 44000 and 52000 om-1 of naphthalene vapour. The experimental method was the same as in ref. 1 Transition energies and suggested assignments are given in Table 1. The bands in this region arise from two n*-r transitions with vibrations built upon them and from two other transitions at 45070 cm-1 and 45390 cm-1 which
