A photoelectron spectroscopic study of the formic acid dimer

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Abstract
The He (I) photoelectron spectrum of the gas‐phase dimer of formic acid, (HCOOH)2, has been measured using a high pressure nozzle inlet system operating at room temperature. Interpretation of the spectrum with the aid of molecular orbital calculations indicates that the dimer shows considerable interaction of the monomer‐based states of σ symmetry, but little interaction of π states. The σ splittings arise mainly from through‐space interactions with the bridging hydrogen atoms making a small contribution to the stability of the lower energy molecular orbital resulting in each case.

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