CRYSTAL14: A Program for the Ab Initio Investigation of Crystalline Solids
CRYSTAL14: A Program for the Ab Initio Investigation of Crystalline Solids
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DOI：
10.1002/qua.24658
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发表时间：
2014-10-05
影响因子：
2.2
通讯作者：
Kirtman, Bernard
中科院分区：
文献类型：
--
作者：
Dovesi, Roberto;Orlando, Roberto;Kirtman, Bernard
介绍了CRYSTAL14程序的功能，并讨论了相对于以前的CRYSTAL09版本所做的改进。CRYSTAL14是一个从头算代码，使用高斯型基集：伪势和全电子策略都是允许的；在元素周期表的第一第二过渡金属行之前，后者并不比前者贵多少。各种密度函数是可用的，包括作为一个极端情况Hartree-Fock；可以使用各种性质的混合（全局、范围分离、双重）。特别是，全局混合的非常有效的实现，例如流行的B3LYP和PBE0处方，允许以相对较低的计算成本执行此类计算。该程序可以在相同的基础上处理零维（分子）、一维（聚合物）、二维（平板）以及三维（3D；晶体）系统。当使用平面波作为基集时，低维系统不需要虚假的三维周期性。对称性在计算的所有步骤中都得到充分利用；例如，这允许以几乎恒定的成本研究半径增加的纳米管（比线性缩放好！）或对（10,10）大小的富勒烯进行自一致场（SCF）计算，其中包含6000个原子，84,000个原子轨道和20个SCF循环，在一个核心上一天。该代码有三种版本：串行、并行和大规模并行。在第二种方法中，最相关的矩阵是重复的，而在第三种方法中，矩阵在倒数空间中是对角化分布的。所有相关的向量在使用后都是动态分配和释放的，这使得CRYSTAL14比以前的版本更加灵活，在以前的版本中，它们是静态分配的。该程序现在更容易适用于低内存机器（就像现在的许多超级计算机一样）。CRYSTAL14可以在并行机器上使用多达大量的核心（基准测试高达10,240个核心），具有良好的可扩展性，主要限制仍然是对角化步骤。许多张量性质可以用一个完全自动化的方式评估，通过使用一个单一的输入关键字：弹性，压电，光弹性，介电，以及第一和第二超极化，电场梯度，伯恩张量等。许多工具允许对结晶化合物的振动特性进行完整的分析。红外和拉曼强度现在可以解析计算，并可以产生相关的光谱。同位素位移很容易评估，只计算一个大系统的一个片段的频率，并确定核对介电张量的贡献。新的算法已被设计用于研究固体解和无序系统。根据分子中原子的量子理论，电子电荷密度的拓扑分析现在通过TOPOND包的集成合并纳入代码中。电子相关可以在Moller-Plesset二阶能级（即MP2）上进行评估，并且通过与CRYSCOR程序的集成合并，目前可以获得一组双杂化。(C) 2014 Wiley期刊公司
The capabilities of the CRYSTAL14 program are presented, and the improvements made with respect to the previous CRYSTAL09 version discussed. CRYSTAL14 is an ab initio code that uses a Gaussian-type basis set: both pseudopotential and all-electron strategies are permitted; the latter is not much more expensive than the former up to the first-second transition metal rows of the periodic table. A variety of density functionals is available, including as an extreme case Hartree-Fock; hybrids of various nature (global, range-separated, double) can be used. In particular, a very efficient implementation of global hybrids, such as popular B3LYP and PBE0 prescriptions, allows for such calculations to be performed at relatively low computational cost. The program can treat on the same grounds zero-dimensional (molecules), one-dimensional (polymers), two-dimensional (slabs), as well as three-dimensional (3D; crystals) systems. No spurious 3D periodicity is required for low-dimensional systems as happens when plane-waves are used as a basis set. Symmetry is fully exploited at all steps of the calculation; this permits, for example, to investigate nanotubes of increasing radius at a nearly constant cost (better than linear scaling!) or to perform self-consistent-field (SCF) calculations on fullerenes as large as (10,10), with 6000 atoms, 84,000 atomic orbitals, and 20 SCF cycles, on a single core in one day. Three versions of the code exist, serial, parallel, and massive-parallel. In the second one, the most relevant matrices are duplicated, whereas in the third one the matrices in reciprocal space are distributed for diagonalization. All the relevant vectors are now dynamically allocated and deallocated after use, making CRYSTAL14 much more agile than the previous version, in which they were statically allocated. The program now fits more easily in low-memory machines (as many supercomputers nowadays are). CRYSTAL14 can be used on parallel machines up to a high number of cores (benchmarks up to 10,240 cores are documented) with good scalability, the main limitation remaining the diagonalization step. Many tensorial properties can be evaluated in a fully automated way by using a single input keyword: elastic, piezoelectric, photoelastic, dielectric, as well as first and second hyperpolarizabilies, electric field gradients, Born tensors and so forth. Many tools permit a complete analysis of the vibrational properties of crystalline compounds. The infrared and Raman intensities are now computed analytically and related spectra can be generated. Isotopic shifts are easily evaluated, frequencies of only a fragment of a large system computed and nuclear contribution to the dielectric tensor determined. New algorithms have been devised for the investigation of solid solutions and disordered systems. The topological analysis of the electron charge density, according to the Quantum Theory of Atoms in Molecules, is now incorporated in the code via the integrated merge of the TOPOND package. Electron correlation can be evaluated at the Moller-Plesset second-order level (namely MP2) and a set of double-hybrids are presently available via the integrated merge with the CRYSCOR program. (C) 2014 Wiley Periodicals, Inc.