Journal
SCIENCE
Volume 298, Issue 5596, Pages 1227-1230Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1076947
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Infrared spectroscopy is used extensively in the study of isolated biomolecules, but it becomes less useful as it is applied to systems of increasing complexity. Even if the individual vibrational bands can be resolved spectroscopically, their assignment becomes problematic when they are more closely spaced than can be determined using ab initio methods. We describe a method that helps to alleviate this difficulty by measuring the direction of the vibrational transition moment for each vibrational band. The molecules of interest ( adenine and cytosine) are cooled to 0.37 kelvin in liquid helium nanodroplets and oriented in a large dc electric field. A polarized infrared laser is then used to determine the directions of the infrared transition moments relative to the permanent dipole moment. Comparisons with ab initio calculations provide detailed structural information, including experimental evidence for nonplanarity of adenine and three tautomers of cytosine.
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