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The B 2 Σ - - X 2 Π 3/2 Transition of AuO Leah O’Brien and Bradley Borchert Southern Illinois University Edwardsville Jim O'Brien, S. Shaji, and Adam Farquhar.

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Presentation on theme: "The B 2 Σ - - X 2 Π 3/2 Transition of AuO Leah O’Brien and Bradley Borchert Southern Illinois University Edwardsville Jim O'Brien, S. Shaji, and Adam Farquhar."— Presentation transcript:

1 The B 2 Σ - - X 2 Π 3/2 Transition of AuO Leah O’Brien and Bradley Borchert Southern Illinois University Edwardsville Jim O'Brien, S. Shaji, and Adam Farquhar University of Missouri - St. Louis

2 Recent Work on AuO Photoelectron Spectroscopy of AuO - and AuOPhotoelectron Spectroscopy of AuO - and AuO Ionization potential of AuO - (EA of AuO)Ionization potential of AuO - (EA of AuO) Spin-orbit splitting in X 2 Π 3/2 state of AuOSpin-orbit splitting in X 2 Π 3/2 state of AuO Vibrational frequenciesVibrational frequencies Ichino et al., J. Chem. Phys. A 108 (2004) 11307-11313Ichino et al., J. Chem. Phys. A 108 (2004) 11307-11313 Microwave Spectroscopy of AuO X 2 Π 3/2Microwave Spectroscopy of AuO X 2 Π 3/2 Precise constants for v=0,1 of X 2 Π 3/2 statePrecise constants for v=0,1 of X 2 Π 3/2 state Okabayashi et al., Chem. Phys. Lett. 403 (2005) 223-227Okabayashi et al., Chem. Phys. Lett. 403 (2005) 223-227 Electronic Spectroscopy of AuO a 4 Σ - 3/2 – X 2 Π 3/2Electronic Spectroscopy of AuO a 4 Σ - 3/2 – X 2 Π 3/2 (0,1) and (1,2) bands near 10726 and 10665 cm -1(0,1) and (1,2) bands near 10726 and 10665 cm -1 Includes ab initio calculation by B. RoosIncludes ab initio calculation by B. Roos O’Brien et al., J. Chem. Phys. A 110 (2006) 11954-11957O’Brien et al., J. Chem. Phys. A 110 (2006) 11954-11957 Electronic Spectroscopy of AuO b 4 Π 3/2 – X 2 Π 3/2Electronic Spectroscopy of AuO b 4 Π 3/2 – X 2 Π 3/2 Previous talk by Jim O’BrienPrevious talk by Jim O’Brien Shaji et al., J. Mol. Spectrosc. 243 (2007) 37–42Shaji et al., J. Mol. Spectrosc. 243 (2007) 37–42

3

4 Experimental Method Hollow cathode sourceHollow cathode source 2-inch gold-lined cathode2-inch gold-lined cathode Helium (3-4 torr) + oxygen (5-8%)Helium (3-4 torr) + oxygen (5-8%) Current set at 0.5 AmpCurrent set at 0.5 Amp Used Intracavity Laser Absorption SpectroscopyUsed Intracavity Laser Absorption Spectroscopy U Missouri – St Louis labU Missouri – St Louis lab Pyrromethene 556 dyePyrromethene 556 dye Recorded 16700-18700 cm -1 regionRecorded 16700-18700 cm -1 region 6 cm -1 per scan6 cm -1 per scan Record background with discharge off for each scanRecord background with discharge off for each scan Divide AuO spectrum by background spectrum to normalizeDivide AuO spectrum by background spectrum to normalize

5 AuO Spectrum

6 AuO Spectrum Recorded Numerous bands identified in 16700-18700 cm -1 regionNumerous bands identified in 16700-18700 cm -1 region Several vibrational progressions that connect with v=0 of the ground stateSeveral vibrational progressions that connect with v=0 of the ground state Previous workPrevious work 17153, 17552, 17933, 18292 and 18624 cm -1 bands17153, 17552, 17933, 18292 and 18624 cm -1 bands Assigned as the (0,0), (1,0), (2,0), (3,0) and (4,0) bands of a new b 4 Π 3/2 – X 2 Π 3/2 transition of AuOAssigned as the (0,0), (1,0), (2,0), (3,0) and (4,0) bands of a new b 4 Π 3/2 – X 2 Π 3/2 transition of AuO This workThis work 16900, 17329, 17745 and 18158 cm -1 bands16900, 17329, 17745 and 18158 cm -1 bands Identified as new progressionIdentified as new progression

7 16900, 17329, 17745 and 18160 cm -1 bands 17329 cm -1 band analyzed first17329 cm -1 band analyzed first 9 branches were identified9 branches were identified 3 sets of P,Q, and R branches were identified that all connected with v=0 of the ground state (confirmed using microwave constants for ground state)3 sets of P,Q, and R branches were identified that all connected with v=0 of the ground state (confirmed using microwave constants for ground state) 6 branches (2 P, 2 Q, and 2 R branches) can be combined using a 2 Σ Hamiltonian for the excited state6 branches (2 P, 2 Q, and 2 R branches) can be combined using a 2 Σ Hamiltonian for the excited state Remaining 3 branches have bandhead near 17345 cm -1, so are not connectedRemaining 3 branches have bandhead near 17345 cm -1, so are not connected

8 AuO Spectrum from ILS

9 J”PePfPf Q ef Q fe ReRe RfRf ObsO-CObsO-CObsO-CObsO-CObsO-CObsO-C 1.5 17329.8200.011 2.5 17329.7620.014 3.5 17329.8200.01517327.0940.02917332.7520.018 4.5 17326.8430.02017324.1220.04417329.762-0.00817326.3800.05317333.2720.031 5.5 17326.1060.00817322.6970.02117329.607-0.01917325.5130.01317333.632-0.017 6.5 17325.236-0.04217321.2060.02017329.327-0.01917324.6300.04517333.937-0.017 7.5 17324.317-0.04117319.600-0.00817328.958-0.01917323.5840.00317334.1900.039 8.5 17323.315-0.02217317.9530.01217328.491-0.01617322.488-0.00217334.190-0.042 9.5 17322.181-0.02417316.179-0.00617327.909-0.01017321.305-0.00317334.190-0.002 10.5 17320.923-0.03817314.339-0.00117327.208-0.17817320.026-0.01117334.009-0.012 11.5 17319.6120.01817312.400-0.00617326.3800.03317318.667-0.01017333.7250.018 12.5 17318.1070.01117310.3830.00017325.2360.03217317.217-0.01017333.2610.02017324.630-0.014 13.5 17316.4720.01417308.268-0.00217324.317-0.02017315.680-0.00817332.6380.03017323.669-0.009 14.5 17314.6880.02217306.057-0.01117323.021-0.10517314.055-0.00517331.786-0.00617322.621-0.003 15.5 17312.7230.01617303.773-0.00517321.4910.01117312.3430.00217330.670-0.10617321.4910.011 16.5 17310.544-0.02217301.4000.00317319.7270.01417310.5440.00917320.2490.004 17.5 17308.124-0.10017298.9330.00517308.6460.00717318.920-0.003 18.5 17296.3750.00617306.6570.00317317.5150.004 19.5 17293.7300.00817304.5850.00617316.0120.003 20.5 17290.9940.00817302.4280.01217314.4200.003 21.5 17288.1700.00917300.1720.01017312.723-0.012

10 Fitting the 17329 cm -1 band Fit as 2 Σ - X 2 Π 3/2 transitionFit as 2 Σ - X 2 Π 3/2 transition In the X 2 Π 3/2 state, the λ-doubling is not resolved, so we can not assign e/f labels to the branchesIn the X 2 Π 3/2 state, the λ-doubling is not resolved, so we can not assign e/f labels to the branches Transition was fit two ways, based on the two possible e/f assignmentsTransition was fit two ways, based on the two possible e/f assignments Two sets of parameters for the excited state were determinedTwo sets of parameters for the excited state were determined

11 Excited State Parameters for 17329 band of AuO, 2 Σ Main difference is spin-rotation parameter for 2 ΣMain difference is spin-rotation parameter for 2 Σ Fit 1 Value EvEv 17329.6919(47) BvBv 0.2878(71) DvDv 0.1350(20) x 10 -4 HvHv -0.9354(20) x 10 -8 γ-1.2646(87) γDγD 0.2052(74) x 10 -3 γHγH 0.1235(25) x 10 -5 Fit 2Value EvEv 17329.0032(48) BvBv 0.2881(62) DvDv 0.1232(18) x 10-4 HvHv -0.9354(20) x 10 -8 γ0.1128(87) γDγD 0.1018(80) x 10 -3 γHγH 0.1123(23) x 10 -5

12 Excited State Assignment: A 2 Σ + or B 2 Σ - ? 2Σ-2Σ- 2Σ+2Σ+ Björn Roos

13 Ab initio Parameters for Excited 2 Σ states (in cm -1 ) A 2 Σ + B 2 Σ - This work TeTeTeTe1439917545~16248* ωeωeωeωe624542.6~440.6* r e (Å) 1.8621.937 r 3 * = 2.001 *assuming the 16900 cm -1 band is the (1,0) band

14 Spin-Rotation in B 2 Σ - State Can we predict γ for the B 2 Σ - state?Can we predict γ for the B 2 Σ - state? 2 Π states interact with the 2 Σ states to make spin-rotation splitting 2 Π states interact with the 2 Σ states to make spin-rotation splitting X 2 Π (0 cm -1, A so ~ -1400 cm -1 )X 2 Π (0 cm -1, A so ~ -1400 cm -1 ) A 2 Σ + (14,000 cm -1 )A 2 Σ + (14,000 cm -1 ) B 2 Σ - (16,600 cm -1 )B 2 Σ - (16,600 cm -1 ) C 2 Π (25,000 cm -1, A so ~ -1400 cm -1 )C 2 Π (25,000 cm -1, A so ~ -1400 cm -1 ) Oh $#!Γ…Oh $#!Γ…

15 When the Going Gets Tough, Call Bob Field! Bob says “We have lots of information…”Bob says “We have lots of information…” Spin rotation is either large and negative or small and positiveSpin rotation is either large and negative or small and positive Spin-rotation splitting arises from a cross term between H rot and H so, so the signs of off-diagonal elements of both H rot and H so enter into the predicted value of the spin-rotation constantSpin-rotation splitting arises from a cross term between H rot and H so, so the signs of off-diagonal elements of both H rot and H so enter into the predicted value of the spin-rotation constant All we need is electronic configurations for 2 Π and 2 Σ states (from Björn Roos)All we need is electronic configurations for 2 Π and 2 Σ states (from Björn Roos)

16 Au AuO X 2 Π O 5d 6s 2p 5dπ 1σ1σ 2σ2σ 3σ3σ 5dδ 2pπ C 2ΠC 2Π A 2Σ+A 2Σ+ B 2Σ-B 2Σ-

17 Spin-Rotation for B 2 Σ - In ProgressIn Progress (THANKS BOB!)(THANKS BOB!)

18 16900, 17329, 17745 and 18160 cm -1 bands Analysis of the 17329 and 17745 cm -1 bands are completedAnalysis of the 17329 and 17745 cm -1 bands are completed Analysis of the 16900 band is underwayAnalysis of the 16900 band is underway Spectra of the 18160 and 18580 cm -1 bands will be recorded Summer 2007Spectra of the 18160 and 18580 cm -1 bands will be recorded Summer 2007 The vibrational assignments are not known: at this time, we are simply assuming that the 16900 cm -1 band is the (1,0) bandThe vibrational assignments are not known: at this time, we are simply assuming that the 16900 cm -1 band is the (1,0) band Roughly based on the calculated separation between the b 4 Π 3/2 and B 2 Σ - statesRoughly based on the calculated separation between the b 4 Π 3/2 and B 2 Σ - states

19 AuO Spectrum from ILS

20 Summary Accomplished:Accomplished: Identified the B 2 Σ - - X 2 Π 3/2 transition in AuOIdentified the B 2 Σ - - X 2 Π 3/2 transition in AuO Analyzed the 17329 and 17745 cm -1 bandsAnalyzed the 17329 and 17745 cm -1 bands To Do:To Do: Estimate spin-rotation parameter for B 2 Σ - stateEstimate spin-rotation parameter for B 2 Σ - state 16900, 18148 and 18580 cm -1 bands16900, 18148 and 18580 cm -1 bands Dunham-type fitDunham-type fit

21 Acknowledgements S. Shaji, UMSL post-doctoral fellowS. Shaji, UMSL post-doctoral fellow Brad Borchert, SIUE undergraduate studentBrad Borchert, SIUE undergraduate student Adam Farquhar, Westminster HS (St. Louis)Adam Farquhar, Westminster HS (St. Louis) Summer 2006 research student at UMSL with STARS program for gifted studentsSummer 2006 research student at UMSL with STARS program for gifted students Bob Field (MIT)Bob Field (MIT) Björn Roos (Lund, Sweden)Björn Roos (Lund, Sweden) FundingFunding NSF (Leah and Jim)NSF (Leah and Jim) PRF (Leah)PRF (Leah) Thank you for your attention!Thank you for your attention!

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