Electrokinetic detection for X-ray spectra of weakly interacting liquids: n-decane and n-nonane

• Published in: The Journal of chemical physics 2014-06, Vol.140 (23), p.234202-234202
• Main Authors: Lam, Royce K, Shih, Orion, Smith, Jacob W, Sheardy, Alex T, Rizzuto, Anthony M, Prendergast, David, Saykally, Richard J
• Format: Article
• Language: English
• Subjects: ABSORPTION; ABSORPTION SPECTROSCOPY; DECANE; DETECTION; Electrokinetics; ELECTRONIC STRUCTURE; ELECTRONS; Ethers; First principles; High vacuum; Hydrocarbons; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; INTERACTIONS; KETONES; LIQUIDS; Microjets; Organic chemistry; Radiation damage; SIGNALS; SOFT X RADIATION; Soft x rays; SOLVENTS; Upstream; Vapor phases; VAPORS; X ray absorption; X ray spectra
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4882901

The introduction of liquid microjets into soft X-ray absorption spectroscopy enabled the windowless study of liquids by this powerful atom-selective high vacuum methodology. However, weakly interacting liquids produce large vapor backgrounds that strongly perturb the liquid signal. Consequently, solvents (e.g., hydrocarbons, ethers, ketones, etc.) and solutions of central importance in chemistry and biology have been inaccessible by this technology. Here we describe a new detection method, upstream detection, which greatly reduces the vapor phase contribution to the X-ray absorption signal while retaining important advantages of liquid microjet sample introduction (e.g., minimal radiation damage). The effectiveness of the upstream detection method is demonstrated in this first study of room temperature liquid hydrocarbons: n-nonane and n-decane. Good agreement with first principles' calculations indicates that the eXcited electron and Core Hole theory adequately describes the subtle interactions in these liquids that perturb the electronic structure of the unoccupied states probed in core-level experiments.