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Angela Y. Chung , Eric  A. Angela Y. Chung , Eric  A.

Angela Y. Chung , Eric A. - PowerPoint Presentation

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Angela Y. Chung , Eric A. - PPT Presentation

Arsenault and Stewart E Novick Nitrogen splittings here there and everywhere A Reinvestigation of the Electronic Properties of 2Bromopyridine with High Resolution Microwave Spectroscopy ID: 634460

bromopyridine mhz calculation mp2 mhz bromopyridine mp2 calculation forti 14n

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Slide1

Angela Y. Chung

, Eric

A. Arsenault, and Stewart E. Novick

Nitrogen splittings here, there, and everywhere:

A Reinvestigation of the Electronic Properties of 2-Bromopyridine with High Resolution Microwave SpectroscopySlide2

High Resolution Microwave Spectroscopy

and 2-bromopyridineSlide3

Predicted Rotational Spectrum

of 2-bromopyridine

Br

81

BrC

5

H

4

N

79

BrC

5

H

4

N

assigned transitionsSlide4

14

N Hyperfine Structure

F

1

 = J + I

1   

(I

1

 =

3/2; spin

of 

79

Br, 

81

Br) 

F

2

 = F

1

 + I

2  

(I

2

 = 1; spin of 14N)

 

*

Caminati, W.; Forti, P. Chem. Phys. Lett. 1972, 15, 343349.

*

*Slide5

Spectroscopic Parameters of

79BrC5H4

Nfrom ab initio and experimentsCaminati, W.; Forti, P. Chem. Phys. Lett.

1972

,

15

, 343349.

MP2/

6-311

++

G(

d,p

)

MP2/

aug

-cc-

pVTZ

(

anharmonic)

Caminati

&

Forti

This work

A

0 /MHz 58865886*5869.7(2)5869.9333(16)B0 /MHz 10201030*1026.139(3)1026.14510(26)C0 /MHz 869876*

873.377(2)

873.37532(20)

DJ /kHz--0.02989*--

0.0308(9)

DJK

/kHz

--

0.203*

--

0.203(11

)DK /kHz--1.08*--1.52(39)d1 /Hz---5.3*---5.3(11)d2 /Hz---0.80*---0.81(19)79Braa /MHz 553.65474.72*552.2(12)551.750(27)79Brbb /MHz -299.43-262.12*-304.4(6)-304.172(21)79Brcc /MHz -254.22-212.60*-248.1(23)-247.578(32)|79Brab| /MHz 0.2885-0.6896*----14Naa /MHz -0.0297-0.15696*---0.085(12)14Nbb /MHz -2.996-2.9440*---3.005(12)14Ncc /MHz 3.0263.1009*--3.090(17)|14Nab|/MHz 2.946-2.7806*--2.98(28)Nlines----44172RMS /kHz----502.5

Br

*

During the conference and in following

communications we

were clarified on an issue with our Gaussian calculations. Specifically that without the keyword “density=current” the calculation would run with the initial calculation

wavefunction

rather than the

wavefunction

of the specified theory level. The

MP2/6-311G++(

d,p

) calculation presented here has been

re-run,

however 

the MP2/

aug

-cc-

pVTZ

calculation is still in progress. We would like to thank Mark Marshall

for his

assistance.Slide6

Spectroscopic Parameters

of 2-bromopyridine

79BrC5H4

N

81

BrC

5

H

4

N

Caminati

&

Forti

This work

Caminati

&

Forti

This

work

A

0

/MHz 5869.7(2)5869.9333(16)5869.9(3)5869.9260(17) B0 /MHz

1026.139(3)1026.14509(25)

1015.526(4)

1015.52827(28) C0

/MHz

873.377(2)

873.37532(20)

865.669(3)

865.67201(20)

D

J

/kHz--0.0308(9) --0.0304(10)DJK /kHz--0.203(11)-- 0.204(11)DK /kHz--1.53(39)--1.53(38)d1 /Hz---5.2(11)---5.2(12)d2 /Hz---0.81(19)---0.78(20)Braa /MHz 552.2(12)551.750(23)460.4(20)460.899(23)Brbb /MHz -304.4(6)-304.172(19)-252.6(7)-254.098(21)Brcc /MHz -248.1(23)-247.578(32)-207.9(33)-206.801(32)14Naa /MHz ---0.085(12)---0.090(12)14Nbb /MHz ---3.005(12)---3.001(12)14Ncc /MHz --3.090(17)--3.091(17)14Nab /MHz ---2.99(28)---2.73(34)Nlines4417244173RMS /kHz502.550

2.5

Br

Caminati

, W.;

Forti

, P.

Chem. Phys. Lett.

1972

,

15

, 343349.Slide7

Structural Parameters for

2-bromopyridine

Caminati, W.; Forti, P. Chem. Phys. Lett. 1972, 15, 343349.

Br

MP2/

6-311++

G(

d,p

)

MP2/

aug

-cc-

pVTZ

Caminati

&

Forti

This work

C-Br Bond Length

r

0

/Å1.903

1.890

1.88(1)

1.8983(39)

Br NQC Asymmetry Parameter

a

(

79

BrC

5

H4N, 81BrC5H4N)-0.0817, -0.0817-0.1043*, -0.1054*-0.102(4),-0.097(7)-0.1026(5),-0.1026(5)a is a measure of the asymmetry of the nuclear quadrupole coupling tensor, where   *During the conference and in following communications we were clarified on an issue with our Gaussian calculations. Specifically that without the keyword “density=current” the calculation would run with the initial calculation wavefunction rather than the wavefunction of the specified theory level. The MP2/6-311G++(d,p) calculation presented here has been re-run, however  the MP2/aug-cc-pVTZ calculation is still in progress. We would like to thank Mark Marshall for his assistance.Slide8

Pyridine vs. 2-bromopyridine Structural Analysis

MP2/

aug-cc-pVTZ

results /Å

pyridine

2-bromopyridine

pyridine

2-bromopyridine

r

1

1.341

1.325

C-H

1

1.084

1.082

r

2

1.341

1.343

C-H

2

1.082

1.080

r

3

1.393

1.390

C-H

3

1.082

1.081

r

4

1.391

1.393C-H41.0821.079r51.3911.389C-H5 1.084--r61.3931.394 C-Br5--1.890pyridine2-bromopyridineSlide9

Reinvestigation of 2-bromopyridine: Anticipating work Slide10

Acknowledgements

*not pictured above: Robert

Melchreit

Eric A. Arsenault

Angela Y. Chung

Susanna Stephens

Daniel A.

Obenchain

Wilman

Orellana

Stephen A. Cooke

Yoon

Jeong

Choi

Wallace (Pete) Pringle

Stewart E.

Novick

Novick

Group