You could do it like this:
import org.apache.spark.sql.Row
import org.apache.spark.sql.types._
// create rdd from the list
val rdd = sc.parallelize(List(4,5,10,7,2))
// rdd: org.apache.spark.rdd.RDD[Int] = ParallelCollectionRDD[31] at parallelize at <console>:28
// zip the data frame with rdd
val rdd_new = df.rdd.zip(rdd).map(r => Row.fromSeq(r._1.toSeq ++ Seq(r._2)))
// rdd_new: org.apache.spark.rdd.RDD[org.apache.spark.sql.Row] = MapPartitionsRDD[33] at map at <console>:32
// create a new data frame from the rdd_new with modified schema
spark.createDataFrame(rdd_new, df.schema.add("new_col", IntegerType)).show
+----+-------+
|row1|new_col|
+----+-------+
| a| 4|
| b| 5|
| c| 10|
| d| 7|
| e| 2|
+----+-------+