Applications of Gaussian Process Model in Molecular Dynamics University of British Columbia Vancouver, Canada. Roman Krems

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1 Applications of Gaussian Process Model in Molecular Dynamics University of British Columbia Vancouver, Canada Roman Krems Gaussian Process Model for Collision Dynamics of Complex Molecules, Jie Cui and RK, Phys. Rev. Lett. 115, (2015). Gaussian Process Model for Extrapolation of Scattering Observables for Complex Molecules, Jie Cui, Zhiying Li and RK, J. Chem. Phys. 143, (2015). Efficient Non- Parametric Fitting of PES for Polyatomic Molecules with Gaussian Processes, JieCuiand RK, arxiv:

2 Outline Two major problems in molecular dynamics Ø Uncertainties of PESs Ø Numerical complexity of quantum calculations Gaussian Process Model as a tool for interpolation in multi- dimensional spaces Applications of the GP model in molecular dynamics: Ø Efficient fitting of PESs Ø Obtaining scattering observables as functions of individual PES parameters Ø Obtaining scattering observables averaged over PES variations Ø Using classical trajectories to interpolate quantum results Ø Obtaining converged results from unconvergedcalculations Ø Extrapolation of scattering observables from one molecule to another

3 Can quantum dynamical calculations be quantitatively predictive? T. V. Tscherbul and RK, Phys. Rev. Lett. 115, (2015). Reaction cross section (a 0 2 ) Rotational state B C A Rotational state Electric field (kv/cm)

4 Can quantum dynamical calculations be quantitatively predictive? Dynamical calculations are sensitive to potential energy surfaces Potential energy surfaces are inherently inaccurate How to deal with this problem? Average the results over variations of PES

5 Average over variations of the PES Elastic cross section (A 2 ) B e (cm 1 ) Relative probability of elastic scattering and spin depolarization a very important question for experiments on cooling molecules Inelastic cross section (A 2 ) B e (cm 1 ) Molecule molecule collisions in a magnetic field Jie Cui and RK, Phys. Rev. A 88, (2013).

6 Average over variations of the PES Elastic cross section (A 2 ) Inelastic cross section (A 2 ) B e (cm 1 ) B e (cm 1 ) Molecule molecule collisions in a magnetic field Jie Cui and RK, Phys. Rev. A 88, (2013). Error bars are obtained by simple scaling of PES But this does not account for errors in anisotropy Required: analysis of the scattering observables as functions of strength and topology of PES

7 Average over variations of the PES Jie Cui and RK, Phys. Rev. Lett. 115, (2015). But this is a difficult task Even for simple systems, PES is parametrized by tens of parameters It is impossible to compute the dynamical observables as functions of all PES parameters We propose to use the Gaussian Process model to solve this problem

8 Gaussian Process = Gaussian Random Function 2 Random functions Input variable

9 Gaussian Process Model 2 Dynamical observables Input variable

10 Gaussian Process Model 2 Random functions Input variable

11 Gaussian Process Model 2 Constrained random functions Input variable

12 Gaussian Process Model how does it work? Jie Cui and RK, Phys. Rev. Lett. 115, (2015). = (x) with x = x 1,x 2,,x q > Observable Collision energy PES parameters Internal energy Step 1. Calculate the observable at a few points of this multi- dimensional space

13 Gaussian Process Model how does it work? Jie Cui and RK, Phys. Rev. Lett. 115, (2015). Step 2. Estimate correlations between the calculated points Assume some mathematical form for the correlations, e.g., R(x, x 0 )= qy i=1 p 5 xi x 0 1+ i + 5(x i x 0 i )2! i 3! i 2 exp and find the maximum likelihood estimates of the unknown coefficients. p 5 xi x 0 i! i.

14 Jie Cui and RK, Phys. Rev. Lett. 115, (2015). Gaussian Process Model how does it work? X We do this by minimizing the log- likelihood function: logl(! Y n )= 1 2 h i nlogˆ2 +log(det(a)) + n with A = 0 1 R(x 1, x 2 ) R(x 1, x n ) R(x 2, x 1 ) R(x n, x 1 ) 1 1 C A ˆ2(!) = 1 n (Y n ) > A 1 (Y n ) ˆ(!) =(I > A 1 I) 1 I > A 1 Y n

15 Gaussian Process Model how does it work? Jie Cui and RK, Phys. Rev. Lett. 115, (2015). Step 3. Make a prediction of the observable at any desired point x 0 where (x 0 )= + A > 0 A 1 ( ) A 0 =(R(x 0, x 1 ),R(x 0, x 2 ),,R(x 0, x n )) > No analytical fitting of data needed We are using the maximum likelihood estimates of the correlations to make a prediction at a new point of space

16 Applications of Gaussian Process Model in Molecular Dynamics Jie Cui and RK, Phys. Rev. Lett. 115, (2015). Obtaining multi- dimensional potential energy surfaces

17 Gaussian Process Model of multi- dimensional PES Jie Cui and RK, arxiv: = (x) with x = x 1,x 2,,x q > Observable Internal coordinates of molecule Ab initio calculations

18 Gaussian Process Model of multi- dimensional PES Jie Cui and RK, arxiv: Six- dimensional PES for N4 Number of ab initio points RMSE at energy < 100 kcal/mol PES from [1] % ± ± 1.56 GP model ± ± ± ± ± 0.37 [1] Y. Paukku et al, J. Chem. Phys. 139,044309(2013).

19 Gaussian Process Model of multi- dimensional PES Six- dimensional PES for N4 Rel Energy (kcal mol) (a) r B (A ) Jie Cui and RK, arxiv: d=1.4 d=1.6 d=1.8 d=2.4 d=10 Obtained with only 240 ab initio points! No fitting of ab initio data with analytical functions needed!

20 Applications of Gaussian Process Model in Molecular Dynamics Jie Cui and RK, Phys. Rev. Lett. 115, (2015). Obtaining scattering observables as functions of potential energy surface parameters

21 Gaussian Process Model how does it work? Jie Cui and RK, Phys. Rev. Lett. 115, (2015). = (x) with x = x 1,x 2,,x q > Observable Collision energy PES parameters Internal energy Collision energy, internal energy and PES parameters are treated on an equal footing as variable parameters

22 A 10 dimensional problem: Collision lifetimes of C6H6 with Ar Jie Cui and RK, Phys. Rev. Lett. 115, (2015). Predicted Lifetime (ps) Lifetime (ps) Collision energy (cm 1 ) % Computed Lifetime (ps) 100 scattering calculations used to train the model 100 calculations enough to interpolate in 10 dimensional space

23 can be used to compute observables with error bars Lifetime (ps) Collision energy (cm 1 ) Jie Cui and RK, Phys. Rev. Lett. 115, (2015).

24 can be used to analyze sensitivity to individual PES parameters % Jie Cui and RK, Phys. Rev. Lett. 115, (2015).

25 Applications of Gaussian Process Model in Molecular Dynamics Jie Cui and RK, Phys. Rev. Lett. 115, (2015). Interpolating quantum results with classical trajectory calculations

26 Applications of Gaussian Process Model in Molecular Dynamics Jie Cui and RK, Phys. Rev. Lett. 115, (2015). Interpolating quantum results with classical trajectory calculations

27 Interpolating quantum results with classical caclulations Jie Cui and RK, Phys. Rev. Lett. 115, (2015). Quantum calculations are expensive Classical calculations are cheap Can correlations between classical and quantum results be used to interpolate quantum results?

28 Interpolating quantum results with classical caclulations Jie Cui and RK, Phys. Rev. Lett. 115, (2015). For this, we use a two- step Gaussian Process model E( ) = F ( )+G( )+" Gaussian Process to model the classical results Gaussian Process to model the difference between the quantum and classical results

29 Interpolating quantum results with classical calculations Cross section (a.u.) Collision energy (cm -1 ) Red line: GP model trained by a combination of classical and quantum results Jie Cui and RK, Phys. Rev. Lett. 115, (2015).

30 Applications of Gaussian Process Model in Molecular Dynamics Extrapolation of dynamical observables from one molecule to another Jie Cui and RK, Phys. Rev. Lett. 115, (2015).

31 Extrapolation of dynamical observables Jie Cui, Zhiying Li and RK, J. Chem. Phys. 143, (2015). Consider two molecules N C benzene benzonitrile

32 Extrapolation of dynamical observables Jie Cui, Zhiying Li and RK, J. Chem. Phys. 143, (2015). What is the effect of the H CN substitution? Can we answer this question without computing the PES for benzonitrile?

33 Extrapolation of dynamical observables Jie Cui, Zhiying Li and RK, J. Chem. Phys. 143, (2015). PES benzonitrile = PES benzene + f(α) α = (α 1, α 2,, α q ) unknown parameters

34 Collisions of benzonitrile with He Ω (A 2 ) benzene benzonitrile Collision energy (cm 1 ) Jie Cui, Zhiying Li and RK, J. Chem. Phys. 143, (2015).

35 Conclusions Gaussian Process model is an excellent tool for interpolation in multi- dimensional spaces Multiple parameters Observable Can be used to obtain the dependence of the observable on each of the input parameters Ø Very easy to implement Ø No need to fit any data with analytical functions Ø Can be applied to systems with up to 100 parameters

36 Conclusions Jie Cui and RK, Phys. Rev. Lett. 115, (2015). Enormous potential for applications in molecular dynamics Makes constructing (>10-50)- dimensional PES easy Can potentially elevate quantum scattering calculations to become fully predictive (with error bars) Can be used for the inverse scattering problem Can be used to analyze the role of individual atoms in determining the encounter of complex molecules