This action might not be possible to undo. Are you sure you want to continue?

Welcome to Scribd. Sign in or start your free trial to enjoy unlimited e-books, audiobooks & documents.Find out more

Download

Standard view

Full view

of .

Look up keyword

Like this

Share on social networks

0Activity

×

0 of .

Results for: No results containing your search query

P. 1

A6Ratings:

(0)|Views: 0|Likes: 0

Published by jameswhite4321

See more

See less

https://www.scribd.com/doc/96998435/A6

06/13/2012

text

original

Mon. Not. R. Astron. Soc.

000

A

TEX style ﬁle v2.2)

A computed line list for the H

2

D

+

molecular ion

Taha Sochi

and Jonathan Tennyson

†

Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, UK

Accepted —. Received —; in original form —

ABSTRACT

A comprehensive, calculated line list of frequencies and transition probabilities for thesingly deuterated isotopologue of H

+3

, H

2

D

+

, is presented. The line list, called ST1,contains over 22 million rotational-vibrational transitions occurring between more than33 thousand energy levels; it covers frequencies up to 18500 cm

−

1

. All energy levelswith rotational quantum number,

J

, up to 20 are considered, making the line list use-ful for temperatures up to at least 3000 K. About 15% of these levels are fully assignedwith approximate rotational and vibrational quantum numbers. The list is calculatedusing a previously proposed, high accuracy,

ab initio

model and consistency checksare carried out to test and validate the results. These checks conﬁrm the accuracy of the list. A temperature-dependent partition function, valid over a more extended tem-perature range than those previously published, and cooling function are presented.Temperature-dependent synthetic spectra in the frequency range 0

−

10000 cm

−

1

arealso given.

Key words:

molecular spectra, discrete variable representation, H

2

D

+

, infrared,rotation-vibration transitions, line list, partition function, cooling function.

1 INTRODUCTION

H

2

D

+

is one of the simplest polyatomic quantum systems.It consists of two electrons bound to three nuclei (two pro-tons and one deuteron) forming a triangular shape at equi-librium. The molecule is an asymmetric prolate top withthree vibrational modes: breathing (

ν

1

), bending (

ν

2

) andasymmetric stretch (

ν

3

). All these modes are infrared active.H

2

D

+

also possesses a permanent electric dipole moment of about 0.6 D due to the displacement of the center of chargefrom the center of mass. Hence pure rotational transitions,which occur in the far infrared, can occur. This all contrastsstrongly with the non-deuterated H

+3

molecular ion whichhas no allowed rotational spectrum and only one infraredactive vibrational mode.In astrophysical environments, H

2

D

+

is formed by sev-eral reactions; the main one isH

+3

+ HD

→

H

2

D

+

+ H

2

.

(1)As this and other similar formation reactions are exother-mic, the formation of H

2

D

+

in the cold interstellar environ-ment is favored. Consequently, the abundance of this speciescan be greatly enhanced compared to the underlying D/Hratio. As an isotopologue of H

+3

, H

2

D

+

is a major participantin chemical reactions taking place in interstellar medium. Inparticular, it plays a key role in the deuteration processes in

E-mail: t.sochi@ucl.ac.uk

†

E-mail: j.tennyson@ucl.ac.uk

+3

lacks a per-manent dipole moment and hence cannot be detected via ra-dio astronomy, its asymmetrical isotopomers, namely H

2

D

+

and D

2

H

+

, are the most promising tracers of the extremelycold and highly dense interstellar clouds. These species arethe last to remain in gaseous state under these extreme con-ditions with observable pure rotational spectra (Dalgarno

2

D

+

is the more abundant and easier to observe and henceit is the main species to utilize in such astrophysical inves-tigations.Although the existence of H

2

D

+

1992;Boreiko and Betz 1993), it is only rel-
atively recently that the molecule was ﬁrmly detected inthe ISM via one of its rotational transition lines (Stark

2

D

+

spectra (Caselli

2008). In particular these spectra have been used to inves-tigate the mid-plane of proto-planetary disks (Ramos

2005), and the suggestion of possible use as aprobe for the presence of the hypothetical cloudlets formingthe baryonic dark matter (Ceccarelli and Dominik 2006).

2

T. Sochi, J. Tennyson

Vibrational transitions of H

2

D

+

have yet to be observed as-tronomically.The potential importance of H

2

D

+

spectroscopy for cos-mology is obvious as it is a primordial molecular specieswhich could have a considerable abundance in the earlyuniverse. In particular it has a potential role in the cool-ing of primordial proto-objects (Dubrovich 1993; Dubrovichand Lipovka 1995; Dubrovich and Partridge 2000;Galli andPalla 1998;Schleicher

2

D

+

in spectral distortions of Cosmic Microwave Back-ground Radiation and whether this can be used to determinethe H

2

D

+

2

D

+

372 GHzline has been considered as a probe for the presence of darkmatter(Ceccarelli and Dominik 2006).Due to its fundamental and astrophysical importance,H

2

D

+

has been the subject of a substantial number of spec-troscopic studies. The ﬁrst successful spectroscopic investi-gation of H

2

D

+

was carried out byShy

(1981) wherenine rotational-vibrational transitions were measured in theinfrared region between 1800 and 2000 cm

−

1

using Doppler-tuned fast-ion laser technique, but no speciﬁc spectroscopicassignments were made. This was followed by other spec-troscopic investigations which include the observation andidentiﬁcation of the strong and highly-important rotational1

10

−

1

11

transition line of ortho-H

2

D

+

10

−

1

11

line of H

2

D

+

with improved accuracy, as well as the 3

21

−

3

22

lineat 646.430 GHz. The three fundamental vibrational bands of the H

2

D

+

ion were observed byAmano and Watson(1984),
Amano(1985)andFoster

ν

2

and 2

ν

3

and to combination

ν

2

+

ν

3

in jet-cooledH

2

D

+

ions.Hlavenka

2

D

+

using cavity ringdownabsorption spectroscopy. Other spectroscopic investigationsinclude those of Asvany

2

D

+

2

12

−

1

11

line at2.363 THz, alongside three more far-infrared lines of H

2

D

+

,using tunable far-infrared spectrometry. However, none of these studies measured absolute line intensities, althoughthe work of F´arn´ık

2

D

+

line lists have been generatedfrom

ab initio

et al

’s list extends to rotational level

J

= 30 and covers alllevels up to 5500cm

−

1

above the ground state. These listswere used in a number of studies for various purposes suchas spectroscopic assignment of energy levels and transitionlines from astronomical observations, and for computationof a low-temperature partition function (Sidhu

1992).The line lists also played an important role in motivatingand steering the experimental and observational work inthis ﬁeld (Miller

2

D

+

line lists suﬀered from limitationsthat include low energy cut-oﬀ and the inclusion of a lim-ited number of levels especially at high

J

. These limitations,alongside the development of high accuracy

ab initio

modelsof H

+3

and its isotopologues, including H

2

D

+

, byPolyanskyand Tennyson (1999), provided the motivation to generate amore comprehensive and accurate line list. The intention isthat the new list will both ﬁll the previous gaps and providedata of better quality.The line list, which we call ST1, consists of 22164810transition lines occurring between 33330 rotational-vibrational levels. These are all the energy levels with ro-tational quantum number

J

20 and frequencies below18500 cm

−

1

. This line list can be seen as a companion tothe H

+3

line list of Neale

(1996) which has been exten-sively used for astrophysical studies; although for reasonsexplained below, the ST1 line list is actually expected to bemore accurate.

2 METHOD

(2004). The code calculates,among other things, wavefunctions, energy levels, transitionlines, dipole moments, and transition probabilities. DVR3Duses an exact Hamiltonian, within the Born-Oppenheimerapproximation, and requires potential energy and dipole sur-faces to be supplied as input. In general, it is these whichlargely determine the accuracy of the resulting calculations(Polyansky

2003).The vibrational stage of the DVR3D suite requires anaccurate model for the variation of electronic potential asa function of nuclear geometry. Here we use the H

+3

ab initio

data of Cencek

(1998) sup-plemented by extra data points; the surface was constrainedat high energy by the data of Schinke

2

D

+

adiabatic correction term ﬁtted byPolyansky andTennyson(1999) to this surface. We also employed Polyan-
sky & Tennyson’s vibrational mass scaling to allow for non-adiabatic corrections to the Born-Oppenheimer approxima-tion: we used

µ

H= 1

.

0075372 u and

µ

D= 2

.

0138140 u forthe vibrational atomic masses, and

µ

H= 1

.

00727647 u and

µ

D= 2

.

01355320 u for the rotational atomic masses. Theaccuracy of this model is assessed below.Calculations were performed in Jacobi coordinates(

r

1

,r

2

,θ

), where

r

1

represents the diatom distance (H-H),

r

2

is the separation of the D atom from the center of massof the diatom, and

θ

is the angle between

r

1

and

r

2

. Radialbasis functions of Morse oscillator type were used to model

r

1

r

2

r

1

were set to

r

e

= 1

.

71,

D

e

= 0

.

10 and

ω

e

= 0

.

0108, with20 Gauss-Laguerre grid points. Parameters of the sphericaloscillator functions were set to

α

= 0

.

0 and

ω

e

= 0

.

0075with 44 Gauss-Laguerre grid points, following extensive testson convergence of the vibrational band origins. 36 Gauss-Legendre grid points were used to represent the angular mo-tion. The ﬁnal vibrational Hamiltonian matrix used was of dimension 2000.In the rotation stage, the size of the Hamiltonian ma-trix, which is a function of

J

, was set to 1800(

J

+1) following

A computed line list for the H

2

D

+

molecular ion

3

Table 1.

Sample of the ST1 levels ﬁle. The columns from left toright are for: index of level in ﬁle,

J

, symmetry, index of level inblock, frequency in cm

−

1

,

v

1

,

v

2

,

v

3

,

J

,

K

a

,

K

c

. We used -2 tomark unassigned quantum numbers.

730 1 4 99 18265.61525 -2 -2 -2 1 1 0731 1 4 100 18379.99989 -2 -2 -2 1 1 0732 1 4 101 18499.05736 -2 -2 -2 1 1 0733 2 1 1 131.63473 0 0 0 2 0 2734 2 1 2 223.86306 0 0 0 2 2 0735 2 1 3 2318.35091 0 1 0 2 0 2736 2 1 4 2427.09231 0 1 0 2 2 0737 2 1 5 2490.93374 0 0 1 2 1 2738 2 1 6 3123.27957 1 0 0 2 0 2739 2 1 7 3209.80678 1 0 0 2 2 0

tests on

J

= 3 and

J

= 15. These tests demonstrated thatchoosing suﬃciently large values for the rotational Hamil-tonian, although computationally expensive, is crucial forobtaining reliable results. Our aim was to obtain conver-gence to within 0.01 cm

−

1

for all rotation-vibration levelsconsidered. Our tests suggest we achieved this except, pos-sibly, for some of the highest lying levels. For these levelsour basic model, and in particular our corrections to theBorn-Oppenheimer approximation, are not reliable to thisaccuracy.To compute the intensity of the vibration-rotation tran-sitions, a dipole moment surface is required. We used the

abinitio

2

D

+

dipole. In the DIPOLE3 module of DVR3D we set the number of Gauss-Legendre quadraturepoints used for evaluating the wavefunctions and dipole sur-face to 50; this choice is consistent with the requirement thatthis parameter should be slightly larger than the number of DVR points used to calculate the underlying wavefunctions.The ﬁnal ST1 line list consists of two main ﬁles: onefor the levels and the other for the transitions. These twoﬁles are constructed and formatted according to the methodand style of the BT2 water line list (Barber

2006). Thetotal amount of CPU time spent in producing the ST1 listincluding preparation, convergence tests, and verifying theﬁnal results is about 8000 hours. We used the serial version of the DVR3D suite on PC platforms running Linux (Red Hat)operating system. Both 32- and 64-bit machines were usedin this work although the ﬁnal data were produced mainlyon 64-bit machines due to the large memory requirement forthe high-

J

calculations.This variational nuclear motion procedure used for thecalculations provides rigorous quantum numbers:

J

, or-tho/para and parity

p

, but not the standard approximatequantum numbers in normal mode, rigid rotor notation. Wehand labelled those levels for which such quantum numberscould be assigned in a fairly straightforward fashion. 5000 of these levels are fully designated with 3 rotational (

J,K

a

,K

c

)and 3 vibrational (

v

1

,v

2

,v

3

) quantum numbers, while 341levels are identiﬁed with rotational quantum numbers only.Some of these assignments are made as initial guess andhence should be treated with caution. Tables1and2present
samples of the ST1 levels and transitions ﬁles respectively.

Table 2.

Sample of the ST1 transitions ﬁle. The ﬁrst two columnsare for the indices of the two levels in the levels ﬁle, while the thirdcolumn is for the

A

coeﬃcients in s

−

1

.

30589 29553 7.99E-0419648 18049 8.37E-038943 7423 5.55E-018490 7981 2.18E-0320620 22169 6.91E-0417613 15937 5.62E-0313046 11400 1.15E-0020639 20054 7.26E-0314433 17117 2.49E-0325960 28074 1.92E-03

Table 3.

Main experimental data sources used to validate theST1 list. Columns 2 and 3 give the number of data points andthe frequency range of the experimental data respectively, whilethe last three columns represent the minimum, maximum, andstandard deviation of discrepancies (i.e. observed minus calcu-lated) in cm

−

1

between the ST1 and the experimental data sets.

Source

N

Range (cm

−

1) Min. Max.

σ

(1981)9 1837 – 1953

−

−

−

0.024 0.054 0.019Foster

−

3 RESULTS AND VALIDATION3.1 Comparison to Experimental and TheoreticalData

We made a number of comparisons between the ST1 line listand laboratory data found in the literature. This enabled usto validate our results. The main sources of laboratory mea-surements that we used in our comparisons are presented inTable3. The table also gives statistical information aboutthe discrepancy between our calculated line frequencies andtheir experimental counterparts. Table4presents a ratherdetailed account of this comparison for a sample data ex-tracted from one of these data sets, speciﬁcally that of As-vany

(2007). This table also contains a comparison of relative Einstein B coeﬃcients between theoretical valuesfrom ST1 and measured values from Asvany

et al

. The the-oretical values in this table are obtained from the calculatedA coeﬃcients using the relation

B

lu

=(2

J

+ 1)

c

3

A

ul

(2

J

+ 1)

l

8

πhν

3

(2)where

A

ul

and

B

lu

are the Einstein A and B coeﬃcientsrespectively for transition between upper (

u

) and lower (

l

)states,

J

and

J

are the rotational quantum numbers forupper and lower states,

h

is Planck’s constant, and

ν

is thetransition frequency.As seen, the ST1 values agree with the measured coef-ﬁcients of Asvany

et al

to within experimental error in allcases. Other comparisons to previous theoretical data, suchas that of Polyansky and Tennyson(1999), were also made
and the outcome was satisfactory in all cases.

- Read and print without ads
- Download to keep your version
- Edit, email or read offline

Are you sure?

This action might not be possible to undo. Are you sure you want to continue?

CANCEL

OK

You've been reading!

NO, THANKS

OK

scribd