Lan Cheng Department of Chemistry The Johns Hopkins University

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Presentation transcript:

Lan Cheng Department of Chemistry The Johns Hopkins University Ab initio calculations of Infrared spectra for XeF6: Isotope shifts and anharmonic contributions Lan Cheng Department of Chemistry The Johns Hopkins University

Experimental studies of XeF6 Electron diffraction experiment (indicating two types of fluorine atoms) Infrared spectra recorded (indicating distortion from Oh structure) No rotational spectra observed Gavin, Bartell, J. Chem. Phys. 48, 2460 (1968); Bartell, Gavin, J. Chem. Phys. 48, 2466 (1968). Kim, Claassen, Pearson, Inorg. Chem. 7, 616 (1968). Falconer, Büchler, Stauffer, Klemperer, J. Chem. Phys. 48, 312 (1968).

Computational efforts SCF calculation with polarization functions favor distorted geometry Relativistic and correlation effects favor the Oh conformer Both structures are local minima on the potential energy surface. Crawford, Springer, Schaefer, J. Chem. Phys. 102, 3307 (1994). Kaupp, van Wüllen, Franke, Schmitz, Kutzelnigg, J. Am. Chem. Soc. 118, 11939 (1996). Dixon, De Jong, Peterson, J. Am. Chem. Soc. 127, 8627 (2005). Cheng, Gauss, Stanton, J. Chem. Phys. 142, 224309 (2015).

Infrared Spectra of XeF6 IR spectrum of 0.3% isotopically pure XeF6 in Ne matrix (Gawrilow, Beckers, Riedel, Free University of Berlin)

Infrared Spectra of XeF6 XeOF4 IR spectrum of 0.3% isotopically pure XeF6 in Ne matrix (Gawrilow, Beckers, Riedel, Free University of Berlin)

Isotope shifts of harmonic frequencies Mode 129XeF6 136XeF6 7 525 524 8 579 578 9 649 646 10 655 652

Isotope shifts of harmonic frequencies Mode 129XeF6 136XeF6 7 525 524 8 579 578 9 649 646 10 655 652

Isotope shifts of harmonic frequencies Mode 129XeF6 136XeF6 7 525 524 8 579 578 9 649 646 10 655 652

Isotope shifts of harmonic frequencies Mode 129XeF6 136XeF6 7 525 524 8 579 578 9 649 646 10 655 652

Isotope shifts of harmonic frequencies Mode 129XeF6 136XeF6 7 525 524 8 579 578 9 649 646 10 655 652

Anharmonic contributions 129XeF6 136XeF6 Mode Harmonic Freq (cm-1) Freq Intensity (km/mol) 1 70 7 525 524 8 579 578 9 649 646 10 655 651.6 1+8 648 Pronounced Fermi resonance for 129XeF6

Anharmonic contributions 129XeF6 136XeF6 Mode Harmonic Freq (cm-1) Freq Intensity (km/mol) 1 70 71 7 525 520 524 518 8 579 570 578 9 649 634 646 632 10 655 637 651.6 1+8 639 648 Pronounced Fermi resonance for 129XeF6

Anharmonic contributions 129XeF6 136XeF6 Mode Harmonic Freq (cm-1) Freq Intensity (km/mol) 1 70 71 7 525 520 273 524 518 281 8 579 570 64 578 67 9 649 634 306 646 632 389 10 655 637 134 651.6 125 1+8 639 55 648 13 Pronounced Fermi resonance for 129XeF6

Infrared Spectra of XeF6 Mode Freq (cm-1) Intensity (km/mol) 7 520 273 518 281 8 570 64 67 9 634 306 632 389 10 637 134 125

Infrared Spectra of XeF6 Mode 7 Xe-F asymmetric stretching 129XeF6 136XeF6 Mode Freq (cm-1) Intensity (km/mol) 7 520 273 518 281 8 570 64 67 9 634 306 632 389 10 637 134 125

Infrared Spectra of XeF6 Mode 8 Xe-F symmetric stretching mixed with umbrella mode 129XeF6 136XeF6 Mode Freq (cm-1) Intensity (km/mol) 7 520 273 518 281 8 570 64 67 9 634 306 632 389 10 637 134 125

Infrared Spectra of XeF6 Mode 9 Xe-F Asymmetric Stretching 129XeF6 136XeF6 Mode Freq (cm-1) Intensity (km/mol) 7 520 273 518 281 8 570 64 67 9 634 306 632 389 10 637 134 125

Outlook Further understanding of the potential energy surface for this molecule Transition state connecting C3v and Oh structures Accurate relative energies of local extrema

Acknowledgements Maxim Gawrilow Helmut Beckers Sebastian Riedel Jaime Combariza Maryland Advanced Research Computing Center DOE