High-resolution UV spectroscopy of 1-indanol

Abstract

We report on rotationally resolved laser induced fluorescence (LIF) and vibrationally resolved resonance enhanced multiphoton ionization (REMPI) spectroscopy of the chiral molecule 1-indanol. Spectra of the S1 ← S0 electronic...

Photoelectron Circular Dichroism as a Signature of Subtle Conformational Changes: The Case of Ring Inversion in 1-Indanol

“…30 The used nomenclature is identical to that of former works. [32][33] The structures previously obtained at the B3LYP-D3BJ/6-31++G(d,p) level were re-optimized at the MP2/6-31++G(d,p) level. Both vertical and adiabatic ionization energies (IE) were determined.…”

“…The two most stable conformational isomers observed under supersonic jet conditions, namely, equatorial (1eq) and axial (2ax), were considered in the calculations . The used nomenclature is identical to that of former works. , The structures previously obtained at the B3LYP-D3BJ/6-31++G­(d,p) level were reoptimized at the MP2/6-31++G­(d,p) level. Both vertical and adiabatic ionization energies (IE) were determined.…”

“…The proposed structures were recently confirmed by high-resolution spectroscopy. 33 The barrier for interconversion was not determined for 1-indanol, but is calculated at 8 to 10 kJ/mol at the MP2/6-31G(d,p) level for the related molecules indan or 2-indanol, a value at the verge of what can be overcome under supersonic jet conditions. 34 In helium, kinetic trapping results in separate trapping of each conformer in its own potential well, while relaxation towards the most stable form is favored in heavier carrier gases.…”

“…It is also more stable by a value ranging from 0.2 kJ/mol at the MP2/aug-cc-pVTZ level to 1.3 kJ/mol at the CCSD­(T)/aug-cc-pVTZ level. The proposed structures were recently confirmed by high-resolution spectroscopy . The barrier for interconversion was not determined for 1-indanol but is calculated at 8–10 kJ/mol at the MP2/6-31G­(d,p) level for the related molecules indan or 2-indanol, a value at the verge of what can be overcome under supersonic jet conditions .…”

Quantitative study of enantiomer-specific state transfer

“…In Step I, a continuous-wave UV laser with an output power up to 80 mW and a bandwidth of < 1 MHz, is used to selectively deplete the population of the target rotational level |1 01 using the |2 02 ← |1 01 R-branch line of the origin band of the S 1 ← S 0 electronic transition [24]. After UV excitation, the molecules predominantly radiate back to higher vibrational levels and to other rotational levels in the S 0 state [25].…”