1. 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

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

3. Literature Studies – Hypermetallic Oxides
Experimental
BeOBe, Heaven et al.1
UV ( nm)
Ground state - 1Σg+
CaOCa, Andrews2,3
Matrix studies, 15K, IR ( 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 = Å
ES linear (3au+), Re = 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)
3 L. Andrews and B.S. Ault, J. Mol. Spec., 68 (1977)
4 B.Ostojic, P. Jensen, P. Schwerdtferger, B. Assadollahzadeh, and P. R. Bunker, J. Mol. Spec. 263 (2010)
5 B.Ostojic, P. R. Bunker, P. Schwerdtferger, B. Assadollahzadeh, and P. Jensen, Phys. Chem. Chem. Phys. 13 (2011)
6 B.Ostojic, P. R. Bunker, P. Schwerdtferger, A. Gertych, and P. Jensen, J. Mol. Str (2012)
7 B.Ostojic, P. Jensen, P. Schwerdtferger, and P. R. Bunker, J. Phys. Chem. A, 117 (2013) 9,370-9,379.

4. LIF Experimental Setupc)
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

5. Initial Survey Scan - CaO* *

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

7. 2nd Survey Scan
CaO
A 1Σ+← X 1Σ+
5-0 (νˈ-νˈˈ)
* - CaOCa ? * * * *

8. Bands of CaOCa
Parallel bands
Perpendicular bands

9. Vibronic Band Fitting - Linear
A1Σ+u ← X 1Σ+g
P(2),P(4)
Tν = 14, (6)
Bν’’= (2)
Bν’ = (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)

10. Linear Geometry Fit 1,2 Tν Bν'' Bνˈ Dν' 14,535 N/A 14,770.019 (6)
(2)
(2)
14, (1)
(4)
(4)
14, (1)
(2)
(2)
14, (8)
(4)
(4)
15, (6)
0.045 (3)
(3)
15, (2)
(5)
(5)
15,126.6 (2)
(9)
(8)
15, (9)
(2)
15, (2)
0.046 (6)
(7)
15, (6)
(2)
*-3.4 x 10-6
15, (1)
(4)
(4)
*-2.8 x 10-6
15,490
15, (2)
(8)
(7)
*-4.7 x 10-6
15, (7)
0.046 (2)
*-1.4 x 10-6
15, (2)
(7)
0.057 (9)
*5.2 x 10-6
1All values are in cm1.
2Uncertainties are in 1σ.
* Statistically insignificant value. Additional fitting parameter.

11. 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

12. Vibronic Band Fitting – Asymmetric Top
A1B2 ← X 1Σ+g
P(2),P(4)
Tν = 14, (4)
Bν’’= (1)
A’ = (fixed)
B’ = (3)
C’ = (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)

13. Linear-to-Bent Geometry Fit1,2,3C'
Dν''
Dν'
14,535
N/A
14, (4)
(1)
(3)
(3)
14, (1)
(5)
(9)
0.046 (1)
14, (1)
(6)
(4)
0.0525(1)
14, (1)
(7)
(1)
(1)
15, (1)
(8)
0.0699(1)
(1)
15, (1)
(5)
(9)
(8)
15, (1)
(4)
(6)
(8)
15, (9)
(7)
(3)
(1)
15, (1)
0.0463(6)
(1)
(1)
15, (2)
0.0462(1)
(2)
(9)
*7.8 x 10-7
*-2.4 x 10-6
15, (1)
0.0472(3)
(7)
(7)
*3.5 x 10-6
15,490
15, (2)
(2)
0.0620(4)
(3)
*-1.1 x 10-6
*-4.7 x 10-6
15, (4)
(4)
(8)
(9)
*2.6 x 10-5
*1.6 x 10-6
15, (2)
(3)
(5)
(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 cm-1
* Statistically insignificant value. Additional fitting parameter.

14. Molecular Constants Study X 1Σg+ / Linear Eq. Geom.
A 1B2 / Bent Eq. Geom. re Be ωe Te
Currenta
2.0337
326
1.9987
342
14,801
Previousb
1.9952
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 (2012)
cLaser Induced Fluorescence Spectroscopy of Jet-Cooled CaOCa, M. Sullivan, D. Frohman, M. Heaven, W. Fawzy, Paper RI10

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

16. 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#