Grounded electronic state spectroscopy

As described at the end of section Al.6.1. in nonlinear spectroscopy a polarization is created in the material which depends in a nonlinear way on the strength of the electric field. As we shall now see, the microscopic description of this nonlinear polarization involves multiple interactions of the material with the electric field. The multiple interactions in principle contain infomiation on both the ground electronic state and excited electronic state dynamics, and for a molecule in the presence of solvent, infomiation on the molecule-solvent interactions. Excellent general introductions to nonlinear spectroscopy may be found in [35, 36 and 37]. Raman spectroscopy, described at the end of the previous section, is also a nonlinear spectroscopy, in the sense that it involves more than one interaction of light with the material, but it is a pathological example since the second interaction is tlirough spontaneous emission and therefore not proportional to a driving field... 

An interesting example occurs in the spectrum of the C2 molecule. The usual rule of absorption spectroscopy is that the transitions originate in the ground electronic state because only it has sufficient population. However, in C2 transitions were observed starting both from a fl state and from a jTstate, so it was not... 

Since the vibrational eigenstates of the ground electronic state constitute an orthonomial basis set, tire off-diagonal matrix elements in equation (B 1.3.14) will vanish unless the ground state electronic polarizability depends on nuclear coordinates. (This is the Raman analogue of the requirement in infrared spectroscopy that, to observe a transition, the electronic dipole moment in the ground electronic state must properly vary with nuclear displacements from... 

Far-infrared and mid-infrared spectroscopy usually provide the most detailed picture of the vibration-rotation energy levels in the ground electronic state. However, they are not always possible and other spectroscopic methods are also important. 

To obtain an accurate value of Tig for the ground electronic state is virtually impossible by vibrational spectroscopy because of the problems of a rapidly decreasing population with increasing v. In fact, most determinations are made from electronic emission spectra from one, or more, excited electronic states to the ground state. 

It is important to realize that electronic spectroscopy provides the fifth method, for heteronuclear diatomic molecules, of obtaining the intemuclear distance in the ground electronic state. The other four arise through the techniques of rotational spectroscopy (microwave, millimetre wave or far-infrared, and Raman) and vibration-rotation spectroscopy (infrared and Raman). In homonuclear diatomics, only the Raman techniques may be used. However, if the molecule is short-lived, as is the case, for example, with CuH and C2, electronic spectroscopy, because of its high sensitivity, is often the only means of determining the ground state intemuclear distance. 

Figure 1.3. Real-time femtosecond spectroscopy of molecules can be described in terms of optical transitions excited by ultrafast laser pulses between potential energy curves which indicate how different energy states of a molecule vary with interatomic distances. The example shown here is for the dissociation of iodine bromide (IBr). An initial pump laser excites a vertical transition from the potential curve of the lowest (ground) electronic state Vg to an excited state Vj. The fragmentation of IBr to form I + Br is described by quantum theory in terms of a wavepacket which either oscillates between the extremes of or crosses over onto the steeply repulsive potential V[ leading to dissociation, as indicated by the two arrows. These motions are monitored in the time domain by simultaneous absorption of two probe-pulse photons which, in this case, ionise the dissociating molecule.

Spectroscopy of the PES for reactions of transition metal (M ) and metal oxide cations (MO ) is particularly interesting due to their rich and complex chemistry. Transition metal M+ can activate C—H bonds in hydrocarbons, including methane, and activate C—C bonds in alkanes [18-20] MO are excellent (and often selective) oxidants, capable of converting methane to methanol [21] and benzene to phenol [22-24]. Transition metal cations tend to be more reactive than the neutrals for two general reasons. First, most neutral transition metal atoms have a ground electronic state, and this... 

Several characteristics of the metal beam have been studied in detail. It is well known that metal clusters and metal oxides are formed as a result of the ablation process. However, these potentially interfering species have been studied in detail130 and it has been concluded that they do not introduce any doubt as to the validity of the experimental results. Much more important than cluster or oxide formation are the atomic electronic state populations of the metal beams. For each metal reactant, these have been characterized using laser-induced fluorescence (LIF) excitation spectroscopy. For Y, only the two spin-orbit states of the ground electronic state (a Dz/2 and a D-3,/2) were observed.123... 

The yttrium monocarbide molecule was only recently observed under high resolution by Simard et al. (37) using Jet-cooled optical spectroscopy. The ground electronic state was determined to be an 0=5/2 state, which was consistent with the ab initio calculations of Shim et al. (38) who predicted a 11 ground state for YC in CASSCF calculations. The experimental work of Simard et al. yielded estimates for both the bond length and harmonic frequency of YC. In addition to their CASSCF calculations. Shim et al. (38) also reported results from mass spectrometric equilibrium experiments, which resulted in a bond dissociation energy of Do = 99.0 3.3 kcal/mol. The results from the present work are shown in Table I. An open-shell coupled cluster singles and doubles... 

Aside from vibration and rotation constants, an important piece of information available from electronic spectra is the dissociation energies of the states involved. In electronic absorption spectroscopy, most of the diatomic molecules will originate from the c"=0 level of the ground electronic state. The vibrational structure of the transition to a given excited electronic state will consist of a series of bands (called a progression) representing changes of 0—>0, 0—>1, 0- 2,..., 0— t nax, where... 

Recall that homonuclear diatomic molecules have no vibration-rotation or pure-rotation spectra due to the vanishing of the permanent electric dipole moment. For electronic transitions, the transition-moment integral (7.4) does not involve the dipole moment d hence electric-dipole electronic transitions are allowed for homonuclear diatomic molecules, subject to the above selection rules, of course. [The electric dipole moment d is given by (1.289), and should be distinguished from the electric dipole-moment operator d, which is given by (1.286).] Analysis of the vibrational and rotational structure of an electronic transition in a homonuclear diatomic molecule allows the determination of the vibrational and rotational constants of the electronic states involved, which is information that cannot be provided by IR or microwave spectroscopy. (Raman spectroscopy can also furnish information on the constants of the ground electronic state of a homonuclear diatomic molecule.)... 

B. Time-Resolved Spectroscopy of Ground Electronic States... 

Recent developments in the field of infrared laser molecular beam spectroscopy have lead to a wealth of information on both the structure (Jucks et al. 1988 Klemperer 1978, 1987 Lovejoy and Nesbitt 1987) and potential energy surfaces (Cohen and Saykally 1991a,b, 1992 Hutson 1988, 1990) associated with these weakly bound molecular complexes in the ground electronic state (Fraser and Pine 1989b Gough et al. 1977 Jucks et al., 1988 Kleiner et al. 1991 Mcllroy et... 

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