Hypertext Dalton 2.0 manual - Theoretical Chemistry, KTH

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CHAPTER 16. VIBRATIONAL CORRECTIONS 119 (ro)vibrational corrections to be calculated for any isotopic species, in the above example for H 2 16 O, HD 16 O, D 2 16 O, H 2 18 O. This is directed by the keyword .ISOTOP. We note that the most abundant isotope will always be calculated, and is therefore not included in the list above. We have requested that rovibrationally averaged geometries be calculated for 5 different temperatures. By default, these geometries will include centrifugal distortions [16]. This can be turned by using the keyword .NO CENT in the *WALK input module. By default, the numerical differentiation will use a step length of 0.0001 bohr. Experience show this to be too short [14], and we have therefore changed this to be 0.001 bohr in the example above by the use of the keyword .DISPLACMENT in the *WALK input module. If only one (or a few) isotopic species are of interest, we can significantly speed up the calculation of the (ro)vibrationally averaged geometries by doing the numerical differentiation in the normal coordinates of the isotopic species of interest. This can be requested through the keyword .NORMAL. The relevant part of the cubic force field is then calculated as numerical second derivatives of analytical gradients. We note that the suggested step length in this case should be set to 0.0075 [14]. We note that we will still need to calculate one analytical Hessian in order to determine the normal coordinates. The default maximum number of iterations is 20. However, dalton will automatically reset the maximum number of iterations to 6K+1 in case of vibrational averaging calculations. The maximum number of iterations can also be set explicitly by using the keyword .MAX IT in the **DALTON INPUT module. 16.2 Vibrational averaged properties The change in the geometry accounts for part of the contribution to a vibrationally averaged property, namely that due to the anharmonicity of the potential [101]. Although this term is important, we need to include also the contribution from the averaging of the molecular property over the harmonic oscillator wave function in order to get an accurate estimate of the vibrational corrections to the molecular property. At the effective geometry, this contribution to for instance the nuclear shielding constants can be obtained from the following input **DALTON INPUT .WALK *WALK .VIBAVE .DISPLACEMENT 0.05 .TEMPERATURES
CHAPTER 16. VIBRATIONAL CORRECTIONS 120 1 300.0 **WAVE FUNCTIONS .HF *SCF INPUT .THRESH 1.0D-10 **START .SHIELD *LINRES .THRESH 1.0D-6 *RESPONS .THRESH 1.0D-5 **EACH STEP .SHIELD *LINRES .THRESH 1.0D-6 *RESPONS .THRESH 1.0D-5 **END OF DALTON INPUT This input will calculate the harmonic contribution to the (ro)vibrational average to the nuclear shielding constants at 300K for 17 ODH. It is important to realize that since each isotopic species for each temperature will have its own unique (ro)vibrationally averaged geometry, we will have to calculate the harmonic contribution for each temperature and each isotopic species separately. The isotopic constitution is specified in the MOLECULE.INP file as described in Chapter 23. We note that we may reuse the property derivatives from a different geometry for calculating the harmonic contribution to the vibrational correction at the given geometry by using the keyword .REUSE in the *WALK module. A new force field is calculated, but the property derivatives are assumed to remain unchanged. The approximation has been tested and been shown to account, through the change in the effective geometry for different temperatures, for a very large fraction of the temperature effects on molecular properties [16]. This calculation will always be done in normal coordinates, and the recommended step length is 0.05 [15]. As for the calculation of (ro)vibrationally averaged geometries in
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DALTON Release 2 Program Manual C.
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CONTENTS ii 5.1.2 A RASSCF calculat
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CONTENTS iv 16 Vibrational correcti
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CONTENTS vi 24.2.17 *STEP CONTROL .
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Preface This is the documentation f
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CHAPTER 1. INTRODUCTION 2 methodolo
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Chapter 2 New features in Dalton 2.
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CHAPTER 2. NEW FEATURES IN DALTON 6
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CHAPTER 2. NEW FEATURES IN DALTON 8
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Part I DALTON Installation Guide 10
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CHAPTER 3. INSTALLATION 12 document
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CHAPTER 3. INSTALLATION 14 Cray), a
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Chapter 4 Maintenance 4.1 Memory re
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CHAPTER 4. MAINTENANCE 18 One may b
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Chapter 5 Getting started with dalt
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CHAPTER 5. GETTING STARTED WITH DAL
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CHAPTER 6. GETTING THE WAVE FUNCTIO
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Chapter 7 Potential energy surfaces
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CHAPTER 7. POTENTIAL ENERGY SURFACE
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Chapter 8 Molecular vibrations In t
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CHAPTER 8. MOLECULAR VIBRATIONS 66
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Page 79 and 80: Chapter 9 Electric properties This
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Page 117 and 118: Chapter 14 Finite field calculation
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CHAPTER 22. INTEGRAL EVALUATION, HE
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Chapter 23 molecule input style The
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CHAPTER 23. MOLECULE INPUT STYLE 18
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Chapter 24 Molecular wave functions
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CHAPTER 24. MOLECULAR WAVE FUNCTION
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Chapter 25 HF, SOPPA, and MCSCF mol
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CHAPTER 25. HF, SOPPA, AND MCSCF MO
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Chapter 26 Linear and non-linear re
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CHAPTER 26. LINEAR AND NON-LINEAR R
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Chapter 27 Coupled-cluster calculat
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CHAPTER 27. COUPLED-CLUSTER CALCULA
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Part IV Appendix: DALTON Tool box 3
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326 A2: labread Author: Hans Jørge
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328 Need 0 0 0 Need 0 0 z Need 0 0
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Bibliography [1] H. J. Aa. Jensen,
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BIBLIOGRAPHY 332 [28] T. Helgaker,
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BIBLIOGRAPHY 334 [56] K. Ruud, T. H
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BIBLIOGRAPHY 336 [82] K. Ruud, T. H
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BIBLIOGRAPHY 338 [107] C. Angeli, S
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BIBLIOGRAPHY 340 [133] R. van Leeuw
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BIBLIOGRAPHY 342 [168] H. Ågren, O
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BIBLIOGRAPHY 344 [194] W. T. Raynes
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Index **DALTON, 21, 50, 57, 59, 67,
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INDEX 348 .C10LMO, 276 .C10SPH, 275
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INDEX 350 CTOCD-DZ,CTOCD-DZ diamagn
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INDEX 352 eigenvector, 148, 150 ele
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INDEX 354 coordinate system, 48 equ
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INDEX 356 iteration number DIIS, ma
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INDEX 358 .MP2, 70, 73-77, 79, 90,
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INDEX 360 nuclear dipole moment, 10
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INDEX 362 print level, 138 *PRINT L
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INDEX 364 .RESTPP, 267 restricted-u
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INDEX 366 spin-rotation constant, 7
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INDEX 368 amplitude, 101 transition
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