Linear dichroism spectroscopy of gas phase biological molecules embedded in superfluid helium droplets

Abstract

This article presents the current status of gas phase linear dichroism (LD) spectroscopy, including the theoretical background, the experimental technique, and a few examples in the UV/VIS and IR. Orientation and alignment of gas phase samples are achieved using a DC electric field. To reach the necessary degree of alignment, biological molecules vaporized from a heated oven need to be embedded in superfluid helium droplets. Excitation under different polarization directions of the light source relative to the alignment field can then be used to derive the direction of the transition dipole, or the size of the permanent dipole, or both. For biological molecules that have no resonance lines or too many resonance lines, LD offers an additional parameter for spectroscopic assignment and tautomeric and conformational identification. The direction of the vibrational transition dipole is proven more reliable for vibrational and tautomeric assignment than the energy or frequency information, which is often problematic because of its sensitivity to basis sets and calculation methods. Several examples of vibrational LD of nucleic acid bases will be discussed. On the other hand, if a chromophore with a known electronic transition dipole is attached to a biological molecule, as demonstrated in the case of tryptamine, the permanent dipole determined from LD is then representative of the molecular conformation. This method of conformational determination does not rely on detailed spectroscopic assignment, thus it is applicable to molecules that do not have resolvable vibronic bands. However, its application is currently limited to the availability of an effective chromophore, and the search for such a chromophore is an on-going effort.