thomas halverson and bill poirier [email protected] texas tech university department of physics...
TRANSCRIPT
EXACT QUANTUM DYNAMICSEXACT QUANTUM DYNAMICS
USING PHASE SPACE WAVELETSUSING PHASE SPACE WAVELETS
Thomas Halverson and Bill [email protected] Tech UniversityDepartment of Physics6-9-13
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I. What we mean by exactII.Exponential scaling and
basis truncationIII.Theoretical OverviewIV.Code specificV. ResultsVI.Future work
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Exact Quantum DynamicsExact Quantum Dynamics
Nuclear dynamicsNuclear dynamicsBorn-Oppenheimer ApproximationBound statesRovibrational Spectroscopy
TISE:TISE:Exact to numerical convergenceIn general, all quantities of interest can be calculated from the eigenfunctions and eigenenergies
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Choice of potentialProblem specificAb initio methods/ DFT
Basis ChoiceDirect product vs. not-direct product
Symmetry• Point group• Permutation/ Inversion
Exponential ScalingDiagonalization Method
Exact Quantum DynamicsExact Quantum Dynamics
Choice of potentialChoice of potential
Basis ChoiceBasis Choice
Diagonalization MethodDiagonalization Method
Symmetrized Gaussians
Direct Diagonalization
(in 1-D)(in 1-D)
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Exponential Scaling and Basis TruncationExponential Scaling and Basis Truncation
For a direct product basisdirect product basis, the size of the Hamiltonian matrix grows exponentially with the degrees of freedom (D)
At large dimensionality problems become intractable
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Exponential Scaling and Basis TruncationExponential Scaling and Basis Truncation
A method for decreasing basis size, without decreasing accuracy
Increases basisbasis efficiencyefficiency::Types
Polyad truncationEnergy truncation
Phase space truncationPhase space truncation
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Theoretical OverviewTheoretical Overview
Density operator for lowest K Density operator for lowest K states of a given Hstates of a given H
Weyl symbol: Wigner PDFPhase space region RQuasi-classical approximation*
*B. Poirier and J. C. Light, J. Chem. Phys. 111, 4869 (1999); B. Poirier and J. C. Light, J. Chem. Phys. 113, 211 (2000).
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Theoretical OverviewTheoretical Overview
Density operator in some Density operator in some basisbasis
Phase space Region R’
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R
R’
Theoretical OverviewTheoretical Overview
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Theoretical OverviewTheoretical Overview
Each square is denoted by a two indices (m, n)
The are of each square has area 2 = (double densitydouble density)
The red square is (m=5/2, n=3/2) and is at coordinate (x = 5/2, p = 3/2
*B. Poirier and A. Salam, J. Chem. Phys. 121, 1690 (2004); B. Poirier and A. Salam, J. Chem. Phys. 121, 1704 (2004).
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Theoretical OverviewTheoretical Overview
Collective well-localizedVery small overlap
Can apply phase space truncated
Linearly IndependentReal valued
*B. Poirier and A. Salam, J. Chem. Phys. 121, 1690 (2004); B. Poirier and A. Salam, J. Chem. Phys. 121, 1704 (2004).
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Theoretical OverviewTheoretical Overview
Phase Space Truncation
Weyl-Heisenberg Lattice
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Theoretical OverviewTheoretical Overview
Start with DPB: Start with DPB: Fmn(x) = fm1n1(x1)×fm2n2(x2)×...
Retain:Retain: H(m1Δ, m2Δ,..., n1Δ, n2Δ) < Emax
Defeats Exponential Defeats Exponential ScalingScaling
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Code SpecificsCode Specifics
Stand alone, single codeStand alone, single codeDimension independentMassively Parallel
Utilizes standard dense matrix routines (Scalapack Library)
effective scaling tested up to 4104 cores
Designed for usability
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ResultsResults
Coupled anharmonic oscillatorA=C=0, B=1/2, D=αMultidimensional Hamiltonian is a sum of one-dimensional Hamiltonians + coupling term
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ResultsResults
Basis size
Converged states
Harmonic Oscillator Basis
Symmetrized Gaussians
3% 2% 0.2% 0.06% 3% 2% 0.2% 0.06%
~1000 820 693 336 241 1015(1018) 954(997) 178(312) 31(115)
~3000 1625 1388 703 547 2893(2931) 2755(2812) 456(786) 75(162)
~10000 3885 3361 1857 1526 9231(9378) 8268(8697) 1683(2184) 428(872)
~30000 8769 7984 4543 3876 26466(26918) 23778(24695) 6546(8625) 1775(4351)
~100000 20614 18355 11970 10698 85501(89227) 75691(81625) 20525(24364) 4105(10761)
~175000 -- -- -- -- 150276(150276) 136595(136595) 48416(48416) 25176(25176)
T. Halverson and B. Poirier, J. Chem. Phys. 137, 224101 (2012).
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ResultsResults
Basis size
Converged states
Harmonic Oscillator Basis
Symmetrized Gaussians
3% 2% 0.2% 0.06% 3% 2% 0.2% 0.06%
~1000 820 693 336 241 1015(1018) 954(997) 178(312) 31(115)
~3000 1625 1388 703 547 2893(2931) 2755(2812) 456(786) 75(162)
~10000 3885 3361 1857 1526 9231(9378) 8268(8697) 1683(2184) 428(872)
~30000 8769 7984 4543 3876 26466(26918) 23778(24695) 6546(8625) 1775(4351)
~100000 20614 18355 11970 10698 85501(89227) 75691(81625) 20525(24364) 4105(10761)
~175000 -- -- -- -- 150276(150276) 136595(136595) 48416(48416) 25176(25176)
T. Halverson and B. Poirier, J. Chem. Phys. 137, 224101 (2012).
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ResultsResults
Lowest 100000 Lowest 100000 computed energies computed energies for 3D coupled for 3D coupled harmonic oscillator harmonic oscillator
Solid line- “master list” energies (N = 302 352)
Dotted line- energy truncated HO basis energies (N = 102 340)
Dashed line- PST SG energies (N = 100 016)
T. Halverson and B. Poirier, J. Chem. Phys. 137, 224101 (2012).
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ResultsResults
DimensionalityBasis Size
Cores 2.0% 0.2% 0.06%
8 23925 24 2408 0 0
8 154323 576 88320 128 0
8 211251 1152 160713 652 1
8 242627 1728 203946 2359 11
12 79759 144 66890 12 0
12 175087 1728 168421 21932 3128
16 13321 36 8265 0 0
16 42473 60 32023 0 0
16 117993 576 110264 239 0
T. Halverson and B. Poirier, J. Chem. Phys. 137, 224101 (2012).
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ResultsResults
DimensionalityBasis Size
Cores 2.0% 0.2% 0.06%
8 23925 24 2408 0 0
8 154323 576 88320 128 0
8 211251 1152 160713 652 1
8 242627 1728 203946 2359 11
12 79759 144 66890 12 0
12 175087 1728 168421 21932 3128
16 13321 36 8265 0 0
16 42473 60 32023 0 0
16 117993 576 110264 239 0
T. Halverson and B. Poirier, J. Chem. Phys. 137, 224101 (2012).
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ResultsResults
Accuracy,(cm-1)
Number ofStates, K
Efficiency,
K/N1000 35186 60.5%
100 10877 18.7%
10 2272 3.9%
1 140 0.24%
0.1 31 0.05%
Quartic force field Quartic force field by Pouchan group*by Pouchan group*
Accurately Computed States for Accurately Computed States for N=58163 N=58163
SG calculations converged using seven different basis sizes ranging from N=310 to N=102858
*C. Pouchan, M. Aouni, and D. Bégué, Chem. Phys. Lett. 334, 352 (2001).
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ResultsResults
Accuracy,(cm-1)
Number ofStates, K
Efficiency,
K/N1000 35186 60.5%
100 10877 18.7%
10 2272 3.9%
1 140 0.24%
0.1 31 0.05%
Quartic force field Quartic force field by Pouchan group*by Pouchan group*
Accurately Computed States for Accurately Computed States for N=58163 N=58163
SG calculations converged using seven different basis sizes ranging from N=310 to N=102858
*C. Pouchan, M. Aouni, and D. Bégué, Chem. Phys. Lett. 334, 352 (2001).
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ResultsResults
Accuracy,(cm-1)
Number ofStates, K
Efficiency,
K/N1000 85450 40.3%
100 3404 1.6%
10 302 0.14%
1 11 0.005%
0.1 3 0.001%
Quartic force field Quartic force field by Pouchan group*by Pouchan group*
Accurately Computed States for Accurately Computed States for N=212197 N=212197
SG calculations converged using six different basis sizes ranging from N=2042 to N=409582
*C. Pouchan, M. Aouni, and D. Bégué, Chem. Phys. Lett. 334, 352 (2001).
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ResultsResults
Accuracy,(cm-1)
Number ofStates, K
Efficiency,
K/N1000 85450 40.3%
100 3404 1.6%
10 302 0.14%
1 11 0.005%
0.1 3 0.001%
Quartic force field Quartic force field by Pouchan group*by Pouchan group*
Accurately Computed States for Accurately Computed States for N=212197 N=212197
SG calculations converged using six different basis sizes ranging from N=2042 to N=409582
*C. Pouchan, M. Aouni, and D. Bégué, Chem. Phys. Lett. 334, 352 (2001).
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ResultsResults
Accuracy,(cm-1)
Number ofStates, K
Efficiency,
K/N1000 60293 39.99%
100 8192 5.4%
10 1100 0.73%
1 73 0.048%
0.1 3 0.002%
Quartic force field Quartic force field by Pouchan group*by Pouchan group*
Accurately Computed States for Accurately Computed States for N=150786 N=150786
SG calculations converged using six different basis sizes ranging from N=1414 to N=340502
*C. Pouchan, M. Aouni, and D. Bégué, Chem. Phys. Lett. 334, 352 (2001).
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ResultsResults
Accuracy,(cm-1)
Number ofStates, K
Efficiency,
K/N1000 60293 39.99%
100 8192 5.4%
10 1100 0.73%
1 73 0.048%
0.1 3 0.002%
Quartic force field Quartic force field by Pouchan group*by Pouchan group*
Accurately Computed States for Accurately Computed States for N=150786 N=150786
SG calculations converged using six different basis sizes ranging from N=1414 to N=340502
*C. Pouchan, M. Aouni, and D. Bégué, Chem. Phys. Lett. 334, 352 (2001).
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Future WorkFuture Work
1.1. Newer, Larger ClustersNewer, Larger ClustersKraken, Blue Waters
2.2. Newer, Larger PotentialsNewer, Larger PotentialsWork with experimental and
electronic structure groups
3.3. Improve accuracyImprove accuracyPhase space region operators*
*R. Lombardini and B. Poirier, Phys. Rev. E 74, 036705 (2006).
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PersonnelPersonnelPrinciple Investigator
Dr. Bill PoirierFellow Graduate Students
Corey PettyDrew Brandon
SupportSupportRobert A. Welch FoundationNational Science Foundation
OrganizerOrganizerssTerry A. MillerFrank C. DeluciaAnne B. McCoy
Computer Computer ResourcesResourcesTexas Tech University
High Performance Computing Center
University Of Texas-Austin
Texas Advanced Computing Center