Electronic Structure of CaOCa Via Laser Induced Fluorescence (LIF) Michael N. Sullivan*, Daniel J. Frohman, Michael C. Heaven Emory University, Atlanta, GA Wafa Fawzy Murray State University, Murray, Kentucky 71st ISMS June 23, 2016

Motivation Hypermetallic metal oxides, M2O (M=Be, Mg, Ca) Strong 2nd bond Unconventional bonding models Metallic character Small clusters to bulk

Literature Studies – Hypermetallic Oxides Experimental BeOBe, Heaven et al.1 UV (300-370 nm) Ground state - 1Σg+ CaOCa, Andrews2,3 Matrix studies, 15K, IR (400-800 cm-1) Symmetrical, bent CaOCa Theoretical Per Jensen et al. (BeOBe4, MgOMg5, CaOCa6, SrOSr7) FV-CASSCF + MRCISD/RS2C Ca, cc-pwCVQZ-DK O, cc-pCVQZ GS linear (1Σg+), Re = 1.99521 Å ES linear (3au+), Re = 1.99883 Å 1 J. M. Merrit, V.E. Bondeybey, and M.C. Heaven, J. Phys. Chem. A, 113 (2009) 13,300-13,309. 2 D.M. Thomas and L. Andrews, J. Mol. Spec., 50 (1974) 220-234. 3 L. Andrews and B.S. Ault, J. Mol. Spec., 68 (1977) 220-234. 4 B.Ostojic, P. Jensen, P. Schwerdtferger, B. Assadollahzadeh, and P. R. Bunker, J. Mol. Spec. 263 (2010) 21-26. 5 B.Ostojic, P. R. Bunker, P. Schwerdtferger, B. Assadollahzadeh, and P. Jensen, Phys. Chem. Chem. Phys. 13 (2011) 7546-7553. 6 B.Ostojic, P. R. Bunker, P. Schwerdtferger, A. Gertych, and P. Jensen, J. Mol. Str. 1023 (2012) 101-107. 7 B.Ostojic, P. Jensen, P. Schwerdtferger, and P. R. Bunker, J. Phys. Chem. A, 117 (2013) 9,370-9,379.

LIF Experimental Setup c) ablation block prism 0.1% N2O/He focusing lens Ca rod ablation plume ablation plume I2 cell -------- --------- PMT collection optics PMT ablation laser probe laser

Initial Survey Scan - CaO * *

UV Bands of CaO J.T. Stewart, M.N. Sullivan, and M.C. Heaven, J. Mol. Spec., 322 (2016) 18-21.

2nd Survey Scan CaO A 1Σ+← X 1Σ+ 5-0 (νˈ-νˈˈ) * - CaOCa ? * * * *

Bands of CaOCa Parallel bands Perpendicular bands

Vibronic Band Fitting - Linear A1Σ+u ← X 1Σ+g P(2),P(4) Tν = 14,770.019 (6) Bν’’= 0.0457 (2) Bν’ = 0.0623 (2) Temp = ~ 3.5 K R(2) R(4) P(6) R(8) P(8),R(0) R(6) R(10) P(10) R(12) P(12) P(14) P(16)

Linear Geometry Fit 1,2 Tν Bν'' Bνˈ Dν' 14,535 N/A 14,770.019 (6) 0.0457 (2) 0.0623 (2) 14,844.61 (1) 0.0443 (4) 0.0509 (4) 14,899.75 (1) 0.0467 (2) 0.0621 (2) 14,960.485 (8) 0.0453 (4) 0.0607 (4) 15,023.289 (6) 0.045 (3) 0.0601 (3) 15,113.65 (2) 0.0446 (5) 0.0494 (5) 15,126.6 (2) 0.0455 (9) 0.0509 (8) 15,146.479 (9) 0.0583 (2) 15,253.62 (2) 0.046 (6) 0.0535 (7) 15,268.982 (6) 0.0539 (2) *-3.4 x 10-6 15,387.89 (1) 0.0455 (4) 0.0525 (4) *-2.8 x 10-6 15,490 15,502.22 (2) 0.0461 (8) 0.0547 (7) *-4.7 x 10-6 15,615.934 (7) 0.046 (2) *-1.4 x 10-6 15,729.53 (2) 0.0481 (7) 0.057 (9) *5.2 x 10-6 1All values are in cm1. 2Uncertainties are in 1σ. * Statistically insignificant value. Additional fitting parameter.

Electronic Structure Calculations Ab initio studies on the first excited singlet state 1Σu+ / A1B2 Level of theory: SA-FV-CAS(10,12)-MRCISD+Q Basis Set: cc-pwCVQZ-DK (all atoms) MOLPRO 2012 Z (b) X (c) Y (a) Ab Initio Investigations of the Excited Electronic States of CaOCa, W. Fawzy, M. Heaven, Paper TK10

Vibronic Band Fitting – Asymmetric Top A1B2 ← X 1Σ+g P(2),P(4) Tν = 14,770.019 (4) Bν’’= 0.0457 (1) A’ = 2.241796 (fixed) B’ = 0.0714 (3) C’ = 0.0532 (3) Temp = ~ 4K R(2) R(4) P(6) P(8),R(0) R(6) R(8) R(10) P(10) R(12) P(12) P(14) P(16)

Linear-to-Bent Geometry Fit1,2,3 C' Dν'' Dν' 14,535 N/A 14,770.019 (4) 0.0457 (1) 0.0714 (3) 0.0532 (3) 14,844.61 (1) 0.0447 (5) 0.0569 (9) 0.046 (1) 14,899.75 (1) 0.0465 (6) 0.0713 (4) 0.0525(1) 14,960.48 (1) 0.0457 (7) 0.0699 (1) 0.0522 (1) 15,023.28 (1) 0.0454 (8) 0.0699(1) 0.0513 (1) 15,113.65 (1) 0.0449 (5) 0.0554 (9) 0.0438 (8) 15,126.62 (1) 0.0455 (4) 0.0561 (6) 0.0455 (8) 15,146.485 (9) 0.0461 (7) 0.0609 (3) 0.0559 (1) 15,253.63 (1) 0.0463(6) 0.0563 (1) 0.0508 (1) 15,268.97 (2) 0.0462(1) 0.0565 (2) 0.0525 (9) *7.8 x 10-7 *-2.4 x 10-6 15,387.89 (1) 0.0472(3) 0.0631 (7) 0.0448 (7) *3.5 x 10-6 15,490 15,502.21 (2) 0.0457 (2) 0.0620(4) 0.0470 (3) *-1.1 x 10-6 *-4.7 x 10-6 15,615.99 (4) 0.0498 (4) 0.0670 (8) 0.0514 (9) *2.6 x 10-5 *1.6 x 10-6 15,729.49 (2) 0.0497 (3) 0.0622 (5) 0.0560 (5) *4.8 x 10-5 *4.3 x 10-5 1All values are in cm1. 2Uncertainties are in 1σ. 3Rotational constant A‘ was fixed to 2.2418 cm-1 * Statistically insignificant value. Additional fitting parameter.

Molecular Constants Study X 1Σg+ / Linear Eq. Geom. A 1B2 / Bent Eq. Geom. re Be ωe Te Currenta 2.0337 0.05096 326 1.9987 0.05275 342 14,801 Previousb 1.9952 0.05295 345 N/A Experimentc 2.0956 0.048 1.9758 0.054 14,535* 1 All values in cm-1 *Possible band origin aAb Initio Investigations of the Excited Electronic States of CaOCa, W. Fawzy, M. Heaven, Paper TK10 bOstojic, Bunker, Schwerdtferger, Gertychm and Jensen, J. Mol.Str. 1023 (2012) 101-107. cLaser Induced Fluorescence Spectroscopy of Jet-Cooled CaOCa, M. Sullivan, D. Frohman, M. Heaven, W. Fawzy, Paper RI10

Conclusions Summary Future Work First observation of CaOCa Resolved vibronic bands Initial fitting Future Work Vibronic band identification MgOMg –Preliminary results

Acknowledgements Dr. Michael Heaven Dr. Jacob Stewart Dr. Wafa Fawzy Heaven group Dr. Jiande Han Dr. Kyle Mascaritolo Joshua Bartlett Robert VanGundy Amanda Dermer Mallory Theis Shawn Michael Bressler NSF CHE# 1265586